Документ взят из кэша поисковой машины. Адрес оригинального документа : http://chem.msu.ru/rus/events/mendel-xiv/objects/lesiv.pdf Дата изменения: Tue May 25 11:03:12 2004 Дата индексирования: Mon Apr 11 03:27:58 2016 Кодировка: Windows-1251 Поисковые слова: m 13

XIV - -

N--N-

: IV : ... ..

. .. 2003.



..................................................3 ....................................4 ..............................9 ................................................ 18 .....................................19 ( )...........20

2



() . , N,N-() (BENA)1, - ( 1). 1
2

RNO
ANC

2

O

N

OSiMe

3

O

N

OAlk

SiMe3X NEt3

SiMe3X NEt3

Me3SiO

N

OSiMe

3

BENA Nu Me3SiO E+ Me3SiO Nu O E

N O OSiMe ASENA Nu:

3

N

N

?

BENA : , . . , N,N- , . - N--N- (ASENA), . 3


ASENA BENA, BENA .


, BENA , . BENA - N- 3, . , s- - . BENA : n- N,N-. - ( ). , BENA : ( 1) SN2' ( 2) ( 2)2. 2
N(OSiMe3)2 1 1 OSiMe3 Nu: Nu 3 O Nu: Me3SiO 2 OSiMe3 Nu: N

N

N

N

OSiMe3 Me3SiO

N

OSiMe3

4

Nu 3

Feger Simhen - BENA - SN2' BENA 11. BENA 9. , , , , BENA , (, )8. ,

4


BENA . . , BENA C- N, , , , , . . BENA. 3 3. 3
: N(OTMS) BEN A :
1a
2

N(OSiMe2tBu)

2

1a' N N N SiMe2tBu 2a' 2b N

N-TMS-:
N NTMS 2a NTMS N SiMe2tBu 2b'

:
N N 3a N NOTMS N 3h N NOTMS N N 3a' NOSiMe2tBu N 3h' NOSiMe2tBu

1 2 3 4 5 6 7 8 9 10 11

(t = 20oC) (). 1a + 2a (1:1) 0.5 M CDCl3 170h 1a + 2a' (1:1) . 72h 1a + 2b (1:1) 0.5 M sol. CDCl3 1.7 h 1a + 2b (1:1) 0.5 M sol. CDCl3 1.4 h 1a + 2b (1:1) 0.5 M sol. CDCl3 0.3 h 1a + 2b (1:1) 0.5 M sol. . 0.5h 1a + 2b' (1:1) 0.5 M sol. CDCl3 1.7 h 1a + 2b' (1:1) 0.5 M sol. CDCl3 24 h 1a' + 2b (1:1) without sol. 1a + 2a + 2b 0.5 M sol. CDCl3 (1:1:1) 1.5 h 1a + NCH2Cl2 0.2h (1:1)

(. 1:) 3h (1:0.25) Et3N (1:0.1) Et3N (1:0.1) Me2tBuSiCl (1:0.1) -

( %%; ) 1.5 h 1.2 h 0.15 h . 1.5 h 1.3 3h (93) 3h (89) 3h (97) 3h (85) a) 3h + 3h' (96) (. 3h:3h'=1:9.3) 3h' (97) 3a (27) and 3h (63) 1

5


a

) .

4, , 1' - ( 4)3. 4
N NTMS + N(OTMS)
2



SN2'.

N

O OEt CO2Et 4b EtO O 5 N

CO2Et

CO2Et 1d

2d

OTMS EtO2C EtOH NOH

CO2Et N

O OTMS 6

O 7 67%

- BENA , , 4, . , , BENA ( 5).

6


5
: :
N(OTMS) R1 R
2 2

N + OTMS R N(OTMS)2
2

O + TMS2O + OTMS -

R 4 N

1

1 N

N N TMS + OTMS - + R
2

O

-N

+ R
2

R 1 O-

1

R 4

1

10 TMS N +N R
2

3 TMS N(OTMS) + R R
2 1 2

N

N +N R
2

N

OTMS N R
1

O

+ OTMS -

+ R R
2

R

1

1

11

1

12

4

:
TMS N +N R 12 N O
2

N

OTMS N R
1

N N R
2

OTMS

+ OTMS -

-TMS2O

R

1

10 -4

3

R R
2

1



4

, , 4. , , 4 . , , 10. , - BENA - . BENA , . - 7


BENA, BENA, - . , BENA , 3, 13, ( 7)12. 7
LA Me3SiO N OSiMe3 LA Me3SiO N OSiMe3 -SiMe3OLA Me3SiO N Nu: NOSiMe
3

Nu 3 NOSiMe
3

1

13 OSiMe3 14

3 - 14. , , ( 8). , 3 BENA. , , BENA 14. 8
Me3SiO Nu: N(OSiMe3)2 R
1 1

N

OSiMe3 -OSiMe3 R
2

NO R
1

Nu:2 R R
2 1

NOSiMe3 Nu2 R 3
2

п уть1

R

1

R 1

2

4 Me3SiO SiMe3X п уть2 R
1

N

SiMe3 O+SiMe3 -O(SiMe3) R
2 2

NO+SiMe R
1

3

NOSiMe3 R
1

OSiMe3 R 14
2

R 13

2

8


, 14 - BENA. . , , BENA - . - BENA .


1. . : 5, 5 4+2 6. , , 3 (), 7. , () . , 3 ( 9). , , , , Z- 1. 3 . X-ray .
1

H

13

C,

INEPT, NOE NOISY .

9


9

O NO
2

R R
1

2

CH
2 2

NO

2

R R 1 R R
1

1

BuNH

R R
3

2

2 1

+ R
4

R 2

5

O

N 1

O

LA CH2Cl2

R

3

R
4

R

R

5

O 3a-f

N

O

3 a* a* b** c d e f ***

R1 H H H H H H Me trans - cis

R2 4-OMe-Ph 4-OMe-Ph 4-OMe-Ph Ph 4-OMe-Ph Ph Ph

R3 H H H H H H H

R4 H H H Me Me Me Me

R5 OEt OEt OEt OMe OMe Me OMe

LA SnCl4 Ti(O-iPr)2Cl Ti(O-iPr)2Cl SnCl4 SnCl4 SnCl4 SnCl4

2 2

T, 0C -94 -78 -78 -94 -94 -94 -94

5 min 1h 1h 5 min 5 min 5 min 5 min

1:2 1:5 1:2 1:2 1:2 1:2 1:3 1:2

71% 45% 38% 71% 92% 74% 57%

2. . , (TMSOTf) 3d N--N- (ASENA) 5d 20 -78 0. ASENA : . ASENA , ( 10).

10


10

R R
3

2 1 6

R R SiMe2R X NEt3 R
3

2

R

1

R

4

R

5

O

N

O

R

4

R

5

O

N

OSiMe2R

6

3a-f
3 a* b** c d d d e f 5 R1 R2 R3 R4 H H Me Me Me Me Me Me R5 OEt OEt OMe OMe OMe OMe Me OMe R6 Me Me Me Me Et t Bu Me Me

5a-f
X Br Br Br Br Cl OTf Br Br CH2Cl2, CH2Cl2, CH2Cl2, CH2Cl2, MeCN, CH2Cl2, CH2Cl2, CH2Cl2, -780C, 24h -780C, 24h -780C, 24h -780C, 24h 200C, 72h -780C, 1h -780C, 24h -780C, 24h 5 %% 98% 98% 97% 67% 62% 71% 95% 95%

H 4-OMe-Ph H a* H b** H 4-OMe-Ph H Ph H c H 4-OMe-Ph H d H 4-OMe-Ph H d' H 4-OMe-Ph H d'' H Ph H e Me Ph H f * - trans ** - cis ,



, : () , 4- . . , 3e - . ASENA 5 . 1H, 13C, 29Si INEPT, NOE NOISY; .

3. ASENA. , BENA - N-
8,9,10

( 11).

11


11 N(OSiMe3) O
2

Nu

1

N

Nu

2

NOH Nu
2

, ASENA . , ASENA - 13 14 ( 12). , : , 11 12 TMS- . , , 11, , , 12. , . ASENA TMS- 11, 12.

12


12
R2 + OSiMe3 10 Nu: R5 R4 O N OSiMe3 Nu: R4 O R2 N R2

R

4

R

5

O 5

N Nu

O

R2 Nu R4 OO N R4

R2 Nu O N O-

SiMe3X R2 Nu R4 N O OSiMe3 12 R2 Nu R4 O OH 14 N R4 R4 O

SiMe3X R2 Nu N MeOH NH4F O 11 R2 Nu N 13 OH OSiMe
3

5 a

10

R2

R4 H

R5 OEt



TMS4-OMe-Ph Imidazole TMS4-OMe-Ph b Imidazole TMS4-OMe-Ph d Imidazole TMS4-OMe-Ph d Pyrazole TMS-1,2,3- 4-OMe-Ph d* Triazole d'** TMS-1,2,3- 4-OMe-Ph d* Triazole d'** Morph Ph c Morph 4-OMe-Ph d *-Nu = 1,2,3-triazol-1-yl; **-Nu

CH2Cl2, 20-400C, 3 h H OEt CH2Cl2, 20-400C, 3 h Me OMe CH2Cl2, 20-400C, 3 h Me OMe NEt3, 200C, 24 h 0 Me OMe 20 C, 24 h NEt3, 200C, 24 h 0 Me OMe 20 C, 24 h Me OMe 200C, 24 h = 1,2,3-triazol-2-yl. Me OMe 12d.

TMS 85% 12a 12a 12b 11c 11d 12d 80% 87% 74% 42% 35% 47% 38% -

OH 91% 91% 85% 97% 92% 71% 86% 78% 60% 83%

, - ASENA , 13


5d + 10c 11d, 12d. 17 ( 13). 13
An SiMe3CN NEt3
3





ASENA



.



11 12, 15, 16,

Me3SiO

OMe An MeOH N 15 95% OSiMe3

Me3SiO

OMe An NH2 NO 16 97% MeOH F-, 12h An NH2 NO 17 91%

MeO

O 5d

N

OSiMe

O







,









ASENA. , TBS-ASENA 5d'' , SiMe2Et-ASENA 5d' TMSCN, 15, SiMe2Et-. ( 14).

14


14
Me3Si An SiMe3NC MeO O 5d N OSiMe3 MeO O Me3Si N N C O SiMe
3

CN

NEt3 An

CN

SiMe

3

An

MeO

N OSiMe3 O SiMe3CN

Me3SiO

OMe An

15

N

OSiMe

3

ASENA BENA. ASENA A, - . , , ASENA, , ( 15). 15
Ph N Ph NO N OON O Ph N NSiMe3 SiMe3O N SiMe3O Ph N N

O

N

OSiMe3

5c

A

18

, ? -, ( 16).

15


16
Ph Br O 19 Nu = CN
-

Ph TMSBr O 5c N OSiMe3 LA

Ph

N

O B

+

N

Nu = 1-TMSpyrazole Ph

Ph Nu O 20 N

Nu O N

Yield 76%

20

Yield = 41%

. , , BENA . 17 , 5 19 .
2

R R
3

R SiMe3X R
3

2

X
4

R

4

R

5

O 5

N

OSiMe

3

R

R

5

O 19

N

5,19 R2 Ph c 4-OMe-Ph d 4-OMe-Ph d 4-OMe-Ph d 4-OMe-Ph g

R3 H H H H -(C

R4 Me Me Me Me H2)4-

R5 OMe OMe OMe OMe H

X Br Br Br Cl Br

MeCN, -300C, 0.5 h MeCN, -300C, 0.5 h CH2Cl2, 00C, 1 h MeCN, 00C, 24 h CH2Cl2, 200C, 2 h

cis:trans trans trans trans trans cis

80% 74% 70% 81% 66%

. , ASENA, -, 19 ( 18).

16


18 SiMe3Br Nu SiMe3 Nu+ + BrC

O 5

N

OSiMe

SiMe3 Nu Br3

BrNu O N O

+

Br -Nu: O 19 N

SiMe3

SiMe3 ,

. , . . , , , , , , , . , TMSBr / - 30 0 ASENA ( 19). 19 An N TMSBr O OMe 5d N OSiMe
3

An + OSiMe
3

An

-300C, 24h

O OMe 5d

N

1:1

N O OSiMe OMe 5d*

3

17



1. N-N- N- C- . 2. - ASENA . 3. ASENA N,N-() (BENA).

18



1. A.D. Dilman, A.A. Tishkov, I.M. Lyapkalo, S.L. Ioffe, V.V. Kachala, Yu.A. Strelenko, V.A. Tartakovsky, J. Chem. Soc., Perkin Trans. I, 2000, 2926. 2. A.V. Lesiv, S.L. Ioffe, Yu.A. Strelenko, V.A. Tartakovsky, Helv. Chim. Acta 2002, 85, 3489. 3. V.A. Tartakovsky, S.L. Ioffe, A.D. Dilman, A.A. Tishkov, Russ. Chem. Bull. 2001, 50, 1936 (Engl. ed); 2001, 50, 1850 (Russ ed). 4. A.D. Dilman, S.L. Ioffe, H. Mayr, J. Org. Chem. 2001, 66, 3196. 6. S.E. Denmark, A. Thorarensen, Chem. Rev., 1996, 96, 137. 7. D. Seebach, I.M. Lyapkalo, R. Dahinden, Helv. Chim. Acta 1999, 82,1829. 8. A.D. Dilman, A.A. Tishkov, I.M. Lyapkalo, S.L. Ioffe, Yu.A. Strelenko, V.A. Tartakovsky, Synthesis, 1998, 181. 9. L.M. Makarenkova, I.V. Bliznets, S.L. Ioffe, Yu.A. Strelenko, V.A. Tartakovsky, Russ. Chem. Bull. 2000, 49, 1261 (Engl. ed); 2000, 49, 1265 (Russ. ed). 10. A.V. Lesiv, S.L. Ioffe, Yu.A. Strelenko, I.V. Bliznets, V.A. Tartakovsky, Mend. Commun. 2002, 99. 11. H.Feger, G. Simchen, Lieb. Ann. Chem, 1986, 1456. 12. .. , , 2001 13. Simchen, G., Kober, W. S. Synthesis 1976, 259. 14. Hoover, F. W., Hass, H. B. J. Org. Chem. 1947, 12, 501.

19


( )
(150 oC) Ar. : (, ), (Mg(OMe)2), (CaH2), (CaH2), (CaH2), (CaH2), , 2- (Na), (Na). - Bruker AM-300 . ppm (); s (), d (), t (), q (), m () and br (). - , J, . . (mp) - . Merk silica gel plates QF-254. : (P2O5), (NaOH). Merk Kieselgel 60. : (Gelest and Akros), (Aldrich), (Fluka), (Fluka), (Aldrich), (Aldrich), 1 (Aldrich), (Acros), (Aldrich), (Aldrich), (Aldrich), 1,2,3- (Aldrich), NaCN (Aldrich). : ,13 13, ---,14 ----4-.14 3.
R
3 2 1



R +

2 1

R R LA R
3

R
4

R

4

R

5

O

N

O

R

R

5

O

N

O

3 R1 H a* H b H c H d Me e * - trans

R2 4-OMe-Ph Ph 4-OMe-Ph Ph Ph

R3 H H H H H

R4 H Me Me Me Me

R5 OEt OMe OMe Me OMe

nitro:ene:LA 1:2:1.1 1:2:1.2 1:2:1.2 1:5:1.2 1:2:1.2

C(nitro) 0.13 M 0.2 M 0.2 M 0.2 M 0.2 M

5 min 5 min 5 min 5 min 5 min

T, 0 -94 -94 -94 -94 -94

71% 71% 92% 60% 57%

A: (10 ) CH2Cl2 -780C SnCl4. 5 . , . AcOEt (150 ), . - NaHCO3 (50 )1. 3 AcOEt (50 ). 3 . - NaHCO3 (50 ), Brine. Na2SO4. . 1a-f Et2O. 1g EtOAc:Pe=1:1. . 1 3a, 5 0.5 NaOH MeOH (100 ). . B: Ti(Oi-Pr)4 (4 , 1.20 ) H2Cl2 (5 ) 00 TiCl4 (4 , 0.44 ). 30 . (2 , 390 ) (4 , 0.38 ) H2Cl2 (6 ) -780. 1 -780. 0.5 N - NaOH MeOH (16 ). H2Cl2

20


(100 ), 0.1 N - NaOH (40 ), . - Na2CO3 (60 ). 2 H2l2 (100 ). 2 0.1 N - NaOH (100 ), brine. Na2SO4. . . Rf= 0.21 (EtOAc:Pe=1:1), Rf= 0.12 (EtOAc:Pe=1:1). 240 (45%) 3a 200 (38%) 3a'.
13

CH3

O
12 11 10 9 4 3 + 14

5 8 7 6

CH3 O-

H3C

O

O

N

3a: mp: 103-105 oC (hexane/EtOAc, 1/1) 1 H : (300.13 MHz, 300K, CDCl3) 1.27 (t, J = 7.0, 3 H, H3C(8)), 1.84 (d, J = 1.7, 3 H, H3C(14)), 2.09 (ddd, J = 2.9, 11.1, 13.8, 1 H, H2C(5)), 2.24 (ddd, J = 2.1, 7.4, 13.8, 1 H, H2C(5)), 3.72 (qd, J = 7.0, 9.9, 1 H, H2C(7)), 3.80 (s, 3 H, H3C(13)), 3.82 (ddd, J = 1.7, 7.4, 11.1, 1 H, HC(4)), 4.06 (qd, J = 7.0, 9.9, 1 H, H2C(7)), 5.35 (dd, J = 2.9, 2.1, 1 H, HC(6)), 6.87 (dd, J = 2.5, 6.6, 2 H, HC(10)), 7.10 (dd, J = 2.5, 6.6, 2 H, HC(11)). 13 C : (75.47 MHz, 300K, CDCl3) 15.1 (C(14)), 17.5 (C(8)), 34.5 (C(5)), 39.8 (C(4)), 55.3 (C(13)), 64.9 (C(7)), 101.0 (C(6)), 114.6 (C(10)), 123.4 (C(3)), 129.0 (C(11)), 132.0 (C(9)), 159.0 (C(12)). TLC: Rf 0.21 (hexane/EtOAc, 1/1) [UV] : C14H19NO4 (265.31) : C, 63.38; H, 7.22; N, 5.28 % : C, 63.44; H, 7.29; N, 5.21 %
13

CH3

O
12 11 10 9 4 3 14

5 8 7 6

CH N+ O
-

3

H3C

O

O

3a': mp: 101-103 oC (hexane/EtOAc, 1/1) 1 H : (300.13 MHz, 300K, CDCl3) 1.24 (t, J = 7.0, 3 H, H3C(8)), 1.85 (d, J = 1.7, 3 H, H3C(14)), 2.06 (ddd, J = 5.4, 7.0, 14.0, 1 H, H2C(5)), 2.52 (ddd, J = 4.1, 8.3, 14.0, 1 H, H2C(5)), 3.68 (m, 2 H, HC(4) and H2C(7)), 3.79 (s, 3 H, H3C(13)), 4.08 (qd, J = 7.0, 9.5, 1 H, H2C(7)), 5.35 (dd, J = 5.4, 4.1, 1 H, HC(6)), 6.85 (dd, J = 2.5, 6.6, 2 H, HC(10)), 7.13 (dd, J = 2.5, 6.6, 2 H, HC(11)) 13 C : (75.47 MHz, 300K, CDCl3) 15.0 (C(14)), 17.1 (C(8)), 35.4 (C(5)), 41.5 (C(4)), 55.3 (C(13)), 65.4 (C(7)), 102.2 (C(6)), 114.2 (C(10)), 124.5 (C(3)), 129.5 (C(11)), 131.9 (C(9)), 158.9 (C(12)) TLC: Rf 0.12 (hexane/EtOAc, 1/1) [UV] : C14H19NO4 (265.31) : C, 63.38; H, 7.22; N, 5.28 % : C, 63.70; H, 7.45; N, 5.54 %

21


12 11 10 9 4 5 6 3 + 13

CH N O-

3

H3C O CH O 3
8

7

3b: mp: 78-79 oC (Et2O) 1 H : (300.13 MHz, 300K, CDCl3) 1.51 (s, 3 H, H3C(8)), 1.83 (s, 3 H, H3C(13)), 1.94 (dd, J = 13.6, 11.8, 1 H, H2C(5)), 2.29 (dd, J = 13.6, 7.7, 1 H, H2C(5)), 3.47 (s, 3 H, H3C(7)), 3.82 (dd, J = 11.8, 7.7, 1 H, HC(4)), 7.13 and 7.21-7.38 (2 m, 5 H, 2 HC(10), 2 HC(11), 1 HC(12)). 13 C : (75.47 MHz, 300K, CDCl3) 17.4 (C(13)), 20.9 (C(8)), 40.3 (C(5)), 42.1 (C(5)), 50.2 (C(7)), 103.9 (C(6)), 122.7, 127.6, 127.9, 129.1 (C(9), C(10), C(11), C(12)), 140.1 (C(3)). : C13H17NO3 (235.28) : C, 66.36; H, 7.28; N, 5.95 % : C, 66.15; H, 7.49; N, 5.79 %
11 10 9 8 4 5 6 3 + 12

CH N O
-

3

H

7 3C

CH 7'

O
3

3c: mp: 93-95 oC (Et2O) 1 H : (300.13 MHz, 300K, CDCl3) 1.39 (s, 3 H, H3C(7)), 1.45 (s, 3 H, H3C(7')), 1.85 (s, 3 H, H3C(12)), 1.94 (dd, J = 13.8, 11.2, 1 H, H2C(5)), 2.12 (dd, J = 13.8, 7.9, 1 H, H2C(5)), 3.67 (dd, J = 11.2, 7.9, 1 H, HC(4)), 7.13 and 7.21-7.38 (2m, 5 H, 2 HC(9), 2 HC(10), 1 HC(11)). 13 C : (75.47 MHz, 300K, CDCl3) 17.3 (C(12)), 22.1 and 27.8 (C(7) and C(7')), 41.6 (C(4)), 43.2 (C(5)), 81.2 (C(6)), 121.9, 127.6, 127.8, 129.1 (C(8), C(9), C(10), C(11)), 140.2 (C(3)). : C13H17NO2 (219.28) : C, 71.21; H, 7.81; N, 6.39 % : C, 71.18; H, 7.78; N, 6.20 %
12 11 10 9 4 5 6 3 + 13 14

CH O
-

3

H3C O CH O 3
8

7

N

3d: mp: 87-88 oC (Et2O) 1 H : (300.13 MHz, 300K, CDCl3) 0.89 (t, J = 7.3, 3 H, H3C(14)), 1.43 (s, 3 H, H3C(8)), 1.97 (m, 2 H, 1 H H2C(5) and 1 H H2C(13)), 2.25 (m, 2 H, 1 H H2C(5) and 1 H H2C(13)), 3.39 (s, 3 H, H3C(7)), 3.80 (dd, J = 11.0, 8.1, 1 H, HC(4)), 7.10-7.38 (m, 5 H, 2 HC(10), 2 HC(11), 1 HC(12)). 13 C : (75.47 MHz, 300K, CDCl3) 8.5 (C(14)), 20.8 (C(8)), 24.2 (C(13)), 40.4 (C(5)), 40.9 (C(4)), 50.1 (C(7)); 103.9 (C(6)), 126.9, 127.6, 128.1, 129.0 (C(9), C(10), C(11), C(12)), 140.1 (C(3)).

22


: C14H19NO13 (249.31) : C, 67.45; H, 7.68; N, 5.62 % : C, 67.52; H, 7.66; N, 5.57 %
13

H3C

O
12 11 10 9 4 14

5

CH3 N
3 +

H3C O CH O 3
8

7

6

O-

3f: mp: 115-117 oC (Et2O) 1 H : (300.13 MHz, 300K, CDCl3) 1.51 (s, 3 H, H3C(8)), 1.83 (d, J = 1.5, 3 H, H3C(14)), 1.92 (dd, J = 13.7, 11.8, 1 H, H2C(5)), 2.28 (dd, J = 13.7, 7.9, 1 H, H2C(5)), 3.49 (s, 3 H, H3C(7)), 3.81 (m, 4 H, H3C(13) and HC(4)), 6.85 (d, J = 8.8, 2 H, HC(10)), 7.09 (d, 2 H, HC(11), J = 8.8). 13 C : (75.47 MHz, 300K, CDCl3) 17.3 (C(14)), 20.9 (C(8)), 40.3 (C(5)), 42.1 (C(4)), 50.1 (C(7)), 55.3 (C(13)), 103.8 (C(6)), 114.6, 123.0, 129.0, 131.9 (C(10), C(11), C(9), C(12)), 159.0 (C(3)). : C14H19NO4 (265.31) : C, 63.38; H, 7.22; N, 5.28 % : C, 63.32; H, 7.18; N, 5.42 % ASENA 5

R R
3

2 1 6

R R SiMe2R X NEt3 R
3

2

R

1

R

4

R

5

O 1

N

O

R

4

R

5

O 2

N

OSiMe2R

6

5 a* b** c d d' d'' e f

R1

R2

R3 H H H H H H H H

R4 H H Me Me Me Me Me Me

R5 OEt OEt OMe OMe OMe OMe Me OMe

R6 Me Me Me Me Et t Bu Me Me

X Br Br Br Br Cl OTf Br Br

CH2Cl2, CH2Cl2, CH2Cl2, CH2Cl2, MeCN, CH2Cl2, CH2Cl2, CH2Cl2, -780C, 24h -780C, 24h -780C, 24h -780C, 24h 200C, 72h -780C, 1h -780C, 24h -780C, 24h

H 4-OMe-Ph H 4-OMe-Ph H Ph H 4-OMe-Ph H 4-OMe-Ph H 4-OMe-Ph H Ph Me Ph * - trans ** - cis

5 %% 98% 98% 97% 67% 62% 71% 95% 95%

ASENA TMSBr. (1 ) H2Cl2 (2 ) - 780 NEt3 (1.2 , 0.17 ) TMSBr (1.1 , 0.15 ). 24 . PE (5 ). PE (15 ), H2O (5 ). p-p NaHSO4 (120 , 6 ), H2O (6 ), Brine. (C-). Na2SO4. ASENA PE.

23


ASENA TBSOTf. (1 ) H2Cl2 (2 ) - 780 NEt3 (1.5 , 0.21 ) TBSOTf (1.2 , 0.28 ). 1 . PE (5 ). PE (15 ), H2O (5 ). 2 H2O (6 ), Brine. (C-). Na2SO4. ASENA PE. 1000 / 0.08 torr 5 TBSOH. ASENA 2d TMSCl. (1 , 265 ) H2Cl2 (2 ) 200 NEt3 (1.5 , 0.21 ) TMSCl (1.2 , 0.15 ). 48 . PE (5 ). PE (15 ), H2O (5 ). p-p NaHSO4 (120 , 6 ), H2O (6 ), Brine, . Na2SO4. . PE. 2d (0.2 , 60% ). ASENA 5d'. (1 , 265 ) H3CN (2 ) 200 NEt3 (1.5 , 0.21 ) SiMe2EtCl (1.2 , 0.17 ). 72 . PE (5 ). PE (15 ), H2O (5 ). p-p NaHSO4 (120 , 6 ), H2O (6 ), Brine, . Na2SO4. . 2 (210 , 60% ).
13

CH3

O
12 11 10 9 4 3 14

5 8 7 6

CH2 N
15

H3C

O

O

OSi(CH3)

3

5a: mp: 42-43 oC (hexane) 1 H : (300.13 MHz, 300K, CDCl3) 0.26 (s, 9 H, H3C(15)), 1.26 (t, J = 7.2, 3 H, H3C(8)), 2.10 (ddd, J = 13.1, 4.6, 9.0, 1 H, H2C(5)), 2.23 (ddd, J = 13.1, 5.3, 5.9, 1 H, H2C(5)), 3.57 (dq, J = 14.4, 7.2, 1 H, H2C(7)), 3.80 (s, 3 H, H3C(13)), 3.91-4.05 (m, 2 H, H2C(7) and H2C(14)), 4.10 (br, 1 H, HC(4)), 4.92 (br, 1 H, H2C(14)), 5.09 (dd, J = 4.6, 5.3, 1 H, HC(6)), 6.87 (d, J = 8.4, 2 H, HC(10)), 7.21 (d, J = 8.4, 2 H, HC(11)) 13 C : (75.47 MHz, 300K, CDCl3) -0.8 (C(15)), 15.0 (C(8)), 36.5 (C(5)), 40.2 (C(4)), 55.2 (C(13)), 64.1 (C(7)), 97.2 (C(14)), 99.3 (C(6)), 113.8 (C(10)), 129.5 (C(11)), 132.8 (C(9)), 158.4 (C(12) and C(3)) 29 Si : (59.63 MHz, 300K, CDCl3) 26.62 : C17H27NO4Si (337.49) : C, 60.50; H, 8.06; N, 4.15 % : C, 60.77; H, 8.30; N, 4.15 %
13

CH3

O
12 11 10 9 4 3 14

5 8 7 6

CH2
15

H3C

O

O

N

OSi(CH3)3

5b: mp: 27-28 oC (hexane) 1 H : (300.13 MHz, 320K, CDCl3) 0.27 (s, 9 H, H3C(15)), 1.25 (t, J = 7.2, 3 H, H3C(8)), 2.10 (m, 2 H, H2C(5)); 3.62 (dq, J = 14.2, 7.2, 1 H, H2C(7)), 3.79 (m, 4 H, H3C(13) and HC(4)), 3.96 (dq, J = 14.2, 7.2, 1 H, H2C(7)), 4.05 (s, 1 H, H2C(14)), 4.98 (s, 1 H, H2C(14)), 5.23 (dd, J = 6.4, 6.5, 1 H, HC(6)), 6.86 (d, J = 8.5, 2 H, HC(10)), 7.18 (d, J = 8.5, 2 H, HC(11))

24


C : (75.47 MHz, 300K, CDCl3) -0.7 (C(15)), 15.2 (C(8)), 36.9 (C(5)), 40.2 (C(4)), 55.2 (C(13)), 64.5 (C(7)), 98.9 (C(14)), 99.5 (C(6)), 113.9 (C(10)), 129.5 (C(11)), 132.8 (C(9)), 158.0, 158.6 (C(12) and C(3)) 29 Si : (59.63 MHz, 300K, CDCl3) 26.11 : C17H27NO4Si (337.49) : C, 60.50; H, 8.06; N, 4.15 % : C, 60.52; H, 8.12; N, 4.07 %
13

13

CH3

O
12 11 10 9 4 3 6 14

5 7

CH N

2 15

H3C O

8

CH3

O

OSi(CH3)

3

5d: mp: 68-70 oC (hexane) 1 H : (300.13 MHz, 300K, CDCl3) 0.26 (s, 9 H, H3C(15)), 1.38 (s, 3 H, H3C(8)), 2.00 (dd, J = 12.5, 4.7, 1 H, H2C(5)), 2.09 (dd, J = 12.5, 11.8, 1 H, H2C(5)), 3.41 (s, 3 H, H3C(7)), 3.78 (s, 3 H, H3C(13)), 3.95 (s, 1 H, H2C(14)), 4.02 (br, 1 H, HC(4)), 4.99 (s, 1 H, H2C(14)), 6.84 (d, J = 8.5, 2 H, HC(10)), 7.15 (d, J = 8.5, 2 H, HC(11)) 13 C : (75.47 MHz, 300K, CDCl3) -0.6 (C(15)), 22.4 (C(8)), 40.3 (br, C(4)), 42.5 (C(5)), 49.5 (C(7)), 55.2 (C(13)), 97.7 (br, C(14)), 101.9 (C(6)), 113.9, 129.7 (C(10) and C(11)), 132.4 (C(9)), 158.4, 158.5 (C(12) and C(3)) 29 Si : (59.63 MHz, 300K, CDCl3) 26.18 : C17H27NO4Si (337.49) : C, 60.50; H, 8.06; N, 4.15 % : C, 60.26; H, 7.97; N, 4.02 %
13

CH3

O
12 11 10 9 4 3 6 14

5 7

CH2 OSi
16

15

H3C O

8

CH3

O

N

CH3 15 CH3 CH3
17

5d': 1 H : (300.13 MHz, 297K, CDCl3) 0.21 (s, 6 H, H3C(15)), 0.73 (q, J = 8.0, 2 H, H2C(16)), 1.02 (t, J = 8.0, 2 H, H3C(17)), 1.38 (s, 3 H, H3C(8)), 2.02 (dd, J = 12,5, 4.4, 1 H, H2C(5)) 2.10 (dd, J = 12,5, 11.8, 1 H, H2C(5)), 3.46 (s, 3 H, H3C(7)), 3.80 (s, 3 H, H3C(13)), 3.94 (s, 1 H, H2C(14)), 4.00 (m, 1 H, HC(4)), 5.01 (s, 1 H, H2C(14)), 6.87 (d, J = 8.8, 2 H, HC(10)), 7.18 (d, J = 8.8, 2 H, HC(11)) 13 C : (75.47 MHz, 297K, CDCl3) -2.9, -2.5 (C(15)), 6.7 (C(16)), 7.6 (C(17)), 22.4 (C(8)), 40.2 (br, C(4)), 42.4 (C(5)), 49.5 (C(7)), 55.2 (C(13)), 97.7 (C(14)), 101.8 (C(6)), 113.8 (C (10)), 129.6 (C (11)), 132.4 (C(9)), 158.4 (C(12) and C(3)) 29 Si : (59.63 MHz, 297K, CDCl3) 27.46 : C18H29NO4Si (351.52) : C, 61.50; H, 8.32; N, 3.98 % : C, 61.40; H, 8.37; N, 4.12 %

25


13

CH3

O
12 11 10 9 4 3 6 14

5 7

CH2 OSi
17

15

H3C O

8

CH

O
3

N H3C

17 16

CH3 15 CH3 CH3
17

CH3

5d'': mp: 62-65 oC (hexane) 1 H : (300.13 MHz, 297K, CDCl3) 0.20, 0.30 (2s, 2 H, H3C(15)), 0.99 (s, 9 H, H3C(17)), 1.40 (s, 3 H, H3C(8)), 2.03 (dd, J = 13.1, 5.2, 1 H, H2C(5)), 2.14 (dd, J = 13.1, 12.5, 1 H, H2C(5)), 3.45 (s, 3 H, H3C(7)), 3.70 (s, 3 H, H3C(13)), 4.00 (m, 2 H, H2C(14) and HC(4)), 5.07 (s, 1 H, H2C(14)), 6.87 (d, J = 8.5, 2 H, HC(10)), 7.18 (d, J = 8.5, 2 H, HC(11)) 13 C : (75.47 MHz, 297K, CDCl3) -5.1, -4.5 (C(15)), 18.1 (C(16)), 22.4 (C(8)), 26.1 (C(17)), 40.5 (br, C(4)), 42.5 (C(5)), 49.7 (C(7)), 55.3 (C(13)), 98.0 (br, C(14)), 102.0 (C(6)), 113.9 (C (10)), 129.7 (C (11)), 132.5 (C(9)), 158.5, 158.6 (C(12) and C(3)) 29 Si : (59.63 MHz, 297K, CDCl3) 28.04 : C20H33NO4Si (379.57) : C, 63.29; H, 8.76; N, 3.69 % : C, 63.20; H, 9.00; N, 3.58 %
12 11 10 9 4 5 3 6 13

CH2 N OSi(CH3)3
14

H3C O CHO 3
8

7

5e: mp: 79-80 oC (hexane) 1 H : (300.13 MHz, 275K, CDCl3) 0.26 (s, 9 H, H3C(14)), 1.40 (s, 3H, H3C(8)), 2.07 (dd, J = 13.3, 4.4, 1 H, H2C(5)), 2.12 (dd, J = 13.3, 12.5, 1 H, H2C(5)), 3.49 (s, 1 H, H3C(7)), 3.91 (s, 1 H, H2C(13)), 4.02 (dd, J = 12.5, 4.4, 1 H, HC(4)), 5.01 (s, 1 H, H2C(13)), 7.22-7.40 (m, 5 H, HC(10), HC(11), HC(12)) 13 C : (75.47 MHz, 303K, CDCl3) -0.7 (C(14)), 22.3 (C(8)), 41.0 (C(4)), 42.1 (C(5)), 49.4 (C(7)), 97.6 (C(13)), 101.8 (C(6)), 126.9, 128.4, 128.7 (C(10), C(11), C(12)), 140.3 (C(9)), 158.0 (C(3)) 29 Si : (59.63 MHz, 297K, CDCl3) 26.23 : C16H25NO3Si (307.46) : C, 62.50; H, 8.20; N, 4.56 % : C, 62.56; H, 8.14; N, 4.43 %

26


12 11 10 9 5 7 4 3 6 8 13

CH

2

14 3

H3C O

CH

CH3 14 N O OSi CH
3 16

H3C
16

15 16

CH3

CH3

5e'': mp: 38-39 oC (hexane) 1 H : (300.13 MHz, 320K, CDCl3) 0.25, 0.31 (2s, 6 H, H3C(14)), 1.01 (s, 9 H, H3C(16)), 1.40 (s, 3 H, H3C(8)), 2.11 (dd, J = 13.3, 5.3, 1 H, H2C(5)), 2.19 (dd, J = 13.3, 12.5, 1 H, H2C(5)), 3.48 (s, 3 H, H3C(7), 4.03 (s, 1 H, H2C(13)), 4.10 (dd, J = 12.5, 5.3, 1 H, HC(4)), 5.08 (s, 1 H, H2C(13)), 7.22-7.39 (m, 5 H, HC(10), HC(11), HC(12)) 13 C : (75.47 MHz, 300K, CDCl3) -5.2, -4.7 (C(14)), 18.0 (C(15)), 22.5 (C(8)), 26.0 (C(16)), 40.7 (C(4)), 42.2 (C(5)), 49.5 (C(7)), 98.5 (C(13)), 102.0 (C(6)), 126.8, 128.3, 128.6 (C(10), C(11)) and C(12), 140.7 (C(9)), 158.2 (C(3)) 29 Si : (59.63 MHz, 300K, CDCl3) 27.99 : C19H31NO3Si (349.55) : C, 65.29; H, 8.94; N, 4.01 % : C, 65.34; H, 8.83; N, 4.20 %
11 10 9 8 4 5 7' H3C CHO 3 7 6 3 12

CH2 N OSi(CH3)3
13

5f: 1 H : (300.13 MHz, 300K, CDCl3) 0.27 (s, 9 H, H3C(13)), 1.32, 1.53 (2s, 6 H, H3C(7) and H3C(7')), 1.78 (dd, J = 12.9, 4.9, 1 H, H2C(5)), 2.06 (dd, J = 12.9, 12.8, 1 H, H2C(5)), 3.83 (dd, J = 12.8, 4.9, 1 H, HC(4)), 3.97, 5.00 (2s, 2 H, H2C(12)), 7.24-7.39 (m, 5 H, HC(9), HC(10), HC(11)). 13 C : (75.47 MHz, 300K, CDCl3) -0.7 (C(13)), 23.6, 29.0 (C(7) and C(7')), 42.9 (C(4)), 43.5 (C(5)), 76.9 (C(6)); 97.1 (C(12)), 126.9, 128.4, 128.8 (C(9), C(10) and C(11)), 141.0 (C(8)), 158.4 (C(3)). 29 Si : (59.63 MHz, 300K, CDCl3) 26.17 : C16H25NO2Si (291.47) : C, 65.93; H, 8.65; N, 4.81 % : C, 66.17; H, 8.90; N, 4.54 %

27


12 11 10 14 9 4 5 3 6

CH3
13

H3C O CH 3
8

7

O

N

OSi(CH3)3

15

5g: 1 H : (300.13 MHz, 300K, CDCl3) 0.29 (s, 9 H, H3C(15)), 1.12 (s, 3 H, H3C(8)), 1.33 (d, J = 6.6, 3 H, H3C(14)), 2.32 (dd, J = 13.2, 6.6, 1 H, H2C(5)), 2.50 (dd, J = 13.2, 7.3, 1 H, H2C(5)), 3.29 (s, 3 H, H3C(7)), 4.14 (br, 1 H, HC(4)), 5.18 (q, J = 6.6, 1 H, HC(13)), 7.15-7.45 (m, 5 H, HC(10), HC(11), and HC(12)) 13 C : (75.47 MHz, 300K, CDCl3) -0.6 (C(15)), 23.3 (C(8)), 37.4 (C(14)), 39.7 (C(4)), 40.5 (C(5)), 49.1 (C(7)), 97.2 (C(6)), 115.1 (C(13)), 126.0, 126.8, 126.9 (C(10), C(11) and C(12)), 141.1 (C(9)), 162.3 (C(3)) 29 Si : (59.63 MHz, 300K, CDCl3) 24.43 : C17H27NO3Si (321.49) : C, 63.51; H, 8.47; N, 4.36 % : C, 63.26; H, 8.40; N, 4.12 %
R2
HN O

R2 N OH O N O +

R2 N O NOH O

O OMe

N

OSiMe

3

14c,d ASENA (1 ) CH2Cl2 (1 ml) (1.5 , 0.13 ml). 5 . . 24 . (3 ml), 3 200/ 0.08 torr. EtOAc : PE = 1 : 5. EtOAc : PE = 1 : 10 ( 12).
14c: mp: 117-122 oC (hexane/EtOAc, 10/1)
12

CH

3

O
11 10 9 8 4 3 13 14 15

5 6

N

O

HO
1

7

O CH3

N

H : (300.13 MHz, 300K, DMSO-d6) 1.44 (s, 3 H, H3C(7)), 1.84 (dd, J = 12.4, 12.7, 1 H, H2C(5)), 2.1 - 2.4 (m, 5 H, H2C(14), H2C(5)), 2.58 (d, J = 12.5, 1 H, H2C(13)), 2.76 (d, J = 12.5, 1 H, H2C(13)), 3.51 (m, 4 H, H2C(15)), 3.65 (dd, J = 5.2, 12.7, 1 H, H3C(4)), 3.78 (s, 3 H, H3C(12)), 6.31 (s, 1 H, HO), 6.88 (d, J = 8.5, 2 H, HC(10)), 7.18 (d, J = 8.5, 2 H, HC(9)). 13 C : (75.47 MHz, 300K, CDCl3) 26.9 (C(7)), 35.8 (C(4)), 37.9 (C(5)), 52.2 (C(14)), 54.7 (C(12)), 59.1 (C(13)), 65.8 (C(15)), 94.2 (C(6)), 113.7 (C(10)), 129.0 (C(9)), 132.1 (C(8)), 156.4 and 158.0 (C(3) and C(11)).

28


12

CH3

O
11 10 9 8 4 3 13 14 15

5 7 6

N

O

H3C
1

O

NOH

H : (300.13 MHz, 300K, DMSO-d6) 2.08 (s, 3 H, H3C(7)), 2.1 - 2.4 (m, 4 H, H2C(14)), 2.71 (d, J = 12.5, 1 H, H2C(13)), 2.91 (d, J = 12.5, 1 H, H2C(13)), 3.05 (dd, J = 7.3, 17.1, 1 H, H2C(5)), 3.24 (dd, J = 7.8, 17.1, 1 H, H2C(5)), 3.51 (m, 4 H, H2C(15)), 3.78 (s, 3 H, H3C(12)), 4.71 (dd, J = 7.8, 7.3, 1 H, H3C(4)), 6.80 (d, J = 8.5, 2 H, HC(10)), 7.30 (d, J = 8.5, 2 H, HC(9)), 10.72 (s, 1 H, HO). 13 C : (75.47 MHz, 300K, CDCl3) 29.0 (C(7)), 37.1 (C(4)), 44.6 (C(5)), 52.7 (C(14)), 54.7 (C(12)), 59.3 (C(13)), 65.6 (C(15)), 113.2 (C(10)), 128.7 (C(9)), 132.3 (C(8)), 154.8 and 157.5 (C(3) and C(11)), 205.3 (C(6)). : C17H24N2O4 (320.39) : C, 63.73; H, 7.55; N, 8.74 % : C, 63.70; H, 7.55; N, 8.70 % 14d: mp: 99-103 oC (hexane/EtOAc, 10/1)
11 10 9 8 5 6 4 3 12 13 14

N

O

HO
1

7

O CH3

N

H : (300.13 MHz, 300K, DMSO-d6) 1.49 (s, 3 H, H3C(7)), 1.89 (dd, J = 12.4, 12.5, 1 H, H2C(5)), 2.0 - 2.4 (m, 5 H, H2C(13), H2C(5)), 2.56 (d, J = 12.3, 1 H, H2C(12)), 2.80 (d, J = 12.3, 1 H, H2C(12)), 3.56 (m, 4 H, H2C(14)), 3.79 (dd, J = 5.2, 12.5, 1 H, H3C(4)), 6.44 (s, 1 H, HO), 7.2 - 7.4 (m, 5 H, HC(9), HC(10) and HC(11)). 13 C : (75.47 MHz, 300K, CDCl3) 26.8 (C(7)), 37.0 (C(4)), 37.9 (C(5)), 52.6 (C(13)), 59.7 (C(12)), 66.2 (C(14)), 94.6 (C(6)), 126.6, 128.1, 128.5 (C(9), C(10), C(11)), 140.6 (C(8)), 156.6(C(3)).
11 10 9 8 5 7 6 4 3 12 13 14

N

O

H3C
1

O

NOH

H : (300.13 MHz, 300K, DMSO-d6) 2.12 (s, 3 H, H3C(7)), 2.0 - 2.4 (m, 4 H, H2C(13)), 2.69 (d, J = 12.5, 1 H, H2C(12)), 2.93 (d, J = 12.5, 1 H, H2C(12)), 3.05 (dd, J = 7.3, 17.1, 1 H, H2C(5)), 3.28 (dd, J = 7.8, 17.1, 1 H, H2C(5)), 3.51 (m, 4 H, H2C(14)), 4.79 (dd, J = 7.8, 7.3, 1 H, H3C(4)), 7.2 - 7.4 (m, 5 H, HC(9), HC(10) and HC(11)), 10.81 (s, 1 H, HO). 13 C : (75.47 MHz, 300K, CDCl3)

29


29.8 (C(7)), 37.6 (C(4)), 44.6 (C(5)), 53.0 (C(13)), 59.7 (C(12)), 66.0 (C(14)), 126.1, 127.9, 128.4 (C(9), C(10) and C(11)), 140.7 (C(8)), 154.7 (C(3)), 205.8 (C(6)). : C16H22N2O3 (290.16) : C, 66.18; H, 7.64; N, 9.65 % : C, 66.20; H, 7.40; N, 9.76 %

ASENA, . ASENA (1 , 0.29 g) (1 , 0.14 g) (0.2 , 30 ) . 24 . . 0.38 g (88%) 18.
13 12 7 6 8 5 9 11 10 4 3 14

OSiMe3

N OSiMe
15 18 3

N
17 16

N

18: mp: Oil 1 H : (300.13 MHz, CDCl3) 0.08 (s, 9 H, H3C(9)), 0.25 (s, 9 H, H3C(18)), 1.18 and 1.23 (2s, 6 H, H3C(7) and H3C(8)), 1.93 (dd, J = 13.9, 5.1, 1 H, H2C(5)), 2.28 (dd, J = 13.9, 8.8, 1 H, H2C(5)), 4.85 and 4.99 (2d, J = 14.7, 2 H, H2C(14)), 4.97 (dd, J = 5.1, 8.8, 1 H, HC(4)), 6.20 (dd, J = 1.5, 2.2, 1 H, HC(16)), 7.10 - 7.30 (m, 6 H, HC(11), HC(12), HC(13), HC(15)), 7.51 (d, J = 2.2, HC(17)). 13 C : (75.47 MHz, CDCl3) -0.9 (C(18)), 2.4 (C(9)), 29.5 and 30.7 (C(7) and C(8)), 38.0 (C(4)), 44.2 (C(5)), 52.8 (C(14)), 74.0 (C(6)), 106.0 (C(16)), 127.0, 127.8 and 128.0 (C(11), C(12), C(13)), 129.0 (C(15)), 138.4 (C(10)), 141.2 (C(17)), 161.8 (C(3)). 29 Si : 8.49 (OSi), 25.5 (NOSi) TLC: Rf 0.79 (EtOAc) [UV]
13 12 7 6 8 5 11 10 3 14

4 9 OSiMe3 18

N
15

N
17 16

N

SiMe3O

2: mp: Oil 1 H : (300.13 MHz, CDCl3) 0.05 (s, 9 H, H3C(9)), 0.25 (s, 9 H, H3C(18)), 1.18 and 1.23 (2s, 6 H, H3C(7) and H3C(8)), 1.97 (dd, J = 6.0, 12.0, 1 H, H2C(5)), 2.28 (dd, J = 8.0, 12.0, 1 H, H2C(5)), 4.26 and 4.47 (2d, J = 14.0, 2 H, H2C(14)), 4.37 (dd, J = 8.0, 6.0, 1 H, HC(4)), 6.20 (dd, J = 1.5, 2.2, 1 H, HC(16)), 7.10 - 7.30 (m, 6 H, HC(11), HC(12), HC(13), HC(15)), 7.51 (d, J = 2.2, HC(17)). 13 C : (75.47 MHz, CDCl3) -1.0 (C(18)), 2.4 (C(9)), 29.5 and 30.7 (C(7) and C(8)), 37.6 (C(4)), 41.5 (C(5)), 58.6 (C(14)), 74.0 (C(6)), 106.0 (C(16)), 127.0, 127.8 and 128.0 (C(11), C(12), C(13)), 129.0 (C(15)), 138.4 (C(10)), 141.2 (C(17)), 161.0 (C(3)). 29 Si : 8.49 (OSi), 24.7 (NOSi) TLC: Rf 0.79 (EtOAc) [UV]

30


- ASENA c . ASENA (1 ) (1 ) (0.2 , 30 ) . 24 . . 11(12). ( 12). 11(12). 11 12 (1 ) (5 ) NH4F (3 ). 4 CHCl3 (5 )/H2O (1 ). (3 3 ). . . 14. ( 12).
11

OMe
10 9 8 7 3 4 5 6 2 1 12

N N 15 OSiMe3
14

13

O

N

.

11: mp: oil 1 H : (300.13 MHz, CDCl3) 0.22 (s, 9 H, H3C(15)), 2.02 (s, 3 H, H3C(6)), 2.80 (dd, J =12.5, 13.7, 1 H, H2C(4)), 3.19 (dd, J = 6.6, 13.7, 1 H, H2C(4)), 3.77 (s, 3 H, H3C(11)), 4.71 (d, J = 7.0 , 1 H, H2C(1)), 4.73 (dd, J = 12.5, 6.6 , 1 H, HC(3)), 4.85 (d, J = 7.0, 1 H, H2C(1)), 6.21 (t, J = 1.5 , 1 H, HC(13)), 6.77 (d, J = 8.6, 2 H, HC(9)), 7.02 (d, J = 8.6 , 2 H, HC(8)), 7.32 (d, J = 1.5, 1 H, HC(12)), 7.49 (d, J = 1.5, 1 H, HC(14)). 13 C : (75.47 MHz, CDCl3) -0.7 (C(15)), 29.6 (C(6)), 38.3 (C(3)), 45.2 (C(4)), 53.6 (C(1)), 55.2 (C(11)), 106.3 (C(13)), 113.8 (C(9)), 129.0 (C(8)), 129.7 (C(12)), 130.9 (C(7)), 139.1 (C(14)), 158.4 (C(2)), 159.9 (C(10)), 206.13 (C(6)). 29 Si : (59.63 MHz, CDCl3) 26.40 TLC: Rf 0.64 (EtOAc/HexH, 1/1) [UV]
11

OMe
10 9 8 7 3 4 5 6 2 1 12

N N
14

13

O OH

N

14: mp: oil 1 H : (300.13 MHz, CDCl3) 1.51 (s, 3 H, H3C(6)), 1.89 (dd, J = 12.0, 13.7, 1 H, H2C(4)), 2.36 (dd, J = 7.4, 13.7 , 1 H, H2C(4)), 3.51 (dd, J = 12.0, 7.4, 1 H, HC(3)), 3.80 (s, 3 H, H3C(11)), 4.68 (s, 2 H, H2C(1)), 6.21 (t, J = 1.2, 1 H, HC(13)), 6.82 (d, J = 8.6, 2 H, HC(9)), 6.99 (d, J = 8.6 , 2 H, HC(8)), 7.12 (d, J = 1.2 , 1 H, HC(12)), 7.49 (d, J = 1.2, 1 H, HC(14)). 13 C : (75.47 MHz, CDCl3) 27.3 (C(6)), 36.2 (C(3)), 38.3 (C(4)), 53.8 (C(1)), 55.3 (C(11)), 96.1 (C(5)), 105.8 (C(13)), 114.5 (C(9)), 129.5 (C(12)), 129.9 (C(8)), 130.8 (C(7)), 139.7 (C(14)), 156.2 (C(2)), 159.0 (C(10)).

31


11

OMe
10 9 8 7 3 4 5 6 2 1 12

N
14

O15 OSiMe

N
3

N
13

12b: mp: oil 1 H : (300.13 MHz, CDCl3) 0.15 (s, 9 H, H3C(15)), 1.51 (s, 3 H, H3C(6)), 1.78 (dd, J =13.7, 12.3, 1 H, H2C(4)), 2.14 (dd, J = 13.7, 5.6, 1 H, H2C(4)), 3.28 (dd, J = 5.6, 12.3 , 1 H, HC(3)), 3.78 (s, 3 H, H3C(11)), 4.42 (s, 2 H, H2C(1)), 6.70 (s, 1 H, HC(14)), 6.82 (d, J = 8.6, 2 H, HC(9)), 6.93 (d, J = 8.6, 2 H, HC(8)), 6.99 (s, 2 H, HC(12) and HC(13)). 13 C : (75.47 MHz, CDCl3) 1.6 (C(15)), 27.2 (C(6)), 35.7 (C(3)), 40.1 (C(4)), 48.9 (C(1)), 55.3 (C(11)), 97.0 (C(5)), 114.7 (C(9)), 118.8 (C(14)), 129.4 (C(13)), 129.5 (C(8)), 130.3 (C(7)), 137.5 (C(12)), 155.4 (C(2)), 159.1 (C(10)). 29 Si : (59.63 MHz, CDCl3) 14.82 TLC: Rf 0.48 (EtOAc/HexH, 1/1) [UV]
11

OMe
10 9 8 7 3 4 5 6 2 1 12

N
14 13

O OH

N

N

14b: mp: 122-125 1 H : (300.13 MHz, DMSO-d6) 1.43 (s, 3 H, H3C(6)), 1.82 (dd, J = 13.0, 12.5, 1 H, H2C(4)), 2.07 (dd, J =13.0, 7.6 , 1 H, H2C(4)), 3.48 (dd, J = 12.5, 7.6, 1 H, HC(3)), 3.72 (s, 3 H, H3C(11)), 4.40 (d, J = 6.0, 1 H, H2C(1)), 4.48 (d, J = 6.0, 1 H, H2C(1)) 6.68 (s, 1 H, HO), 6.82 (d, J = 8.9, 2 H, HC(9)), 6.84 (s, 1 H, HC(14)), 6.91 (s, 1 H, HC(13)), 7.09 (d, J = 8.9, 2 H, HC(8)), 7.21 (s, 1 H, HC(12)). 13 C : (75.47 MHz, CDCl3) 26.6 (C(6)), 35.9 (C(3)), 38.7 (C(4)), 48.0 (C(1)), 55.1 (C(11)), 95.2 (C(5)), 114.4 (C(9)), 119.2 (C(14)), 128.3 (C(13)), 129.4 (C(8)), 130.9 (C(7)), 137.3 (C(12)), 154.8 (C(2)), 158.4 (C(10)).
11

OMe
10 9 8 7 3 4 5 6 2 1 12

N OH
14 13

O

N

N

32


13b: H : (300.13 MHz, DMSO-d6) 2.07 (s, 3 H, H3C(6)), 3.10 (m, 1 H, H2C(4)), 3.74 (s, 3 H, H3C(11)), 4.55 (d, J = 7.7, 1 H, H2C(1)), 4.66 (dd, J = 5.6, 7.8, 1 H, HC(3)), 4.67 (d, J = 7.7, 1 H, H2C(1)) 6.84 (d, J = 8.6, 2 H, HC(9)), 6.86 (s, 1 H, HC(14)), 6.89 (s, 1 H, HC(13)), 7.11 (d, J = 8.6, 2 H, HC(8)), 7.44 (s, 1 H, HC(12)), 11.22 (s, 1 H, HO). 13 C : (75.47 MHz, CDCl3) 29.7 (C(6)), 37.0 (C(3)), 43.9 (C(4)), 47.0 (C(1)), 55.0 (C(11)), 113.7 (C(9)), 119.7 (C(14)), 128.0 (C(13)), 128.8 (C(8)), 130.8 (C(7)), 137.6 (C(12)), 154.4 (C(2)), 157.8 (C(10)), 206.1 (C(5)).
1

11

OMe
10 9 8 7 3 4 5 6 2 1

N
13

N N
12

O14 OSiMe

N
3

11d: mp: oil 1 H : (300.13 MHz, CDCl3) 0.12 (s, 9 H, H3C(14)), 1.53 (s, 3 H, H3C(6)), 1.85 (dd, J = 12.8, 11.9, 1 H, H2C(4)), 2.20 (dd, J = 12.8, 6.6, 1 H, H2C(4)), 3.47 (dd, J = 6.6, 11.9, 1 H, HC(3)), 3.80 (s, 3 H, H3C(11)), 4.80 (d, J = 12.0, 1 H, H2C(1)), 5.00 (d, J = 12.0, 1 H, H2C(1)), 6.87 (d, J = 8.7, 2 H, HC(9)), 7.06 (d, J = 8.7, 2 H, HC(8)), 7.42 (s, 1 H, HC(13)), 7.68 (s, 1 H, HC(12)). 13 C : (75.47 MHz, CDCl3) 1.4 (C(14)), 27.2 (C(6)), 36.4 (C(3)), 40.1 (C(4)), 51.7 (C(1)), 55.3 (C(11)), 97.2 (C(5)), 114.7 (C(9)), 123.9 (C(13)), 129.6 (C(8)), 130.1 (C(7)), 133.7 (C(12)), 154.8 (C(2)), 159.1 (C(10)). TLC: Rf 0.18 (EtOAc/HexH, 1/1) [UV]
11

OMe
10 9 8 7 3 4 5 6 2 1

N N

N
12

O 13 OSiMe3

N

11d': mp: oil 1 H : (300.13 MHz, CDCl3) 0.13 (s, 9 H, H3C(13)), 1.52 (s, 3 H, H3C(6)), 1.84 (dd, J = 12.8, 12.0, 1 H, H2C(4)), 2.21 (dd, J = 12.8, 7.0, 1 H, H2C(4)), 3.59 (dd, J = 7.0, 12.0, 1 H, HC(3)), 3.81 (s, 3 H, H3C(11)), 4.98 (s, 2 H, H2C(1)), 6.86 (d, J = 8.6, 2 H, HC(9)), 7.03 (d, J = 8.6, 2 H, HC(8)), 7.55 (s, 2 H, HC(12)). 13 C : (75.47 MHz, CDCl3) 1.4 (C(13)), 27.3 (C(6)), 36.5 (C(3)), 40.2 (C(4)), 55.3 (C(11)), 56.3 (C(1)), 97.0 (C(5)), 114.5 (C(9)), 129.5 (C(8)), 130.7 (C(7)), 134.3 (C(12)), 154.7 (C(2)), 158.9 (C(10)). TLC: Rf 0.51 (EtOAc/HexH, 1/1) [UV]

33


11

OMe
10 9 8 7 3 4 5 6 2 1

N
13

N N
12

O

N

OSiMe

14 3

12d: mp: oil 1 H : (300.13 MHz, CDCl3) 0.23 (s, 9 H, H3C(14)), 2.05 (s, 3 H, H3C(6)), 2.83 (dd, J =14.0, 6.0, 1 H, H2C(4)), 3.31 (dd, J = 14/0, 8.3, 1 H, H2C(4)), 3.75 (s, 3 H, H3C(11)), 4.58 (dd, J = 6.0, 8.3, 1 H, HC(3)), 4.95 (d, J = 11.1, 1 H, H2C(1)), 5.13 (d, J = 11.1, 1 H, H2C(1)), 6.76 (d, J = 8.6, 2 H, HC(9)), 7.04 (d, J = 8.6, 2 H, HC(8)), 7.50 (d, J = 1.8, 1 H, HC(13)), 7.63 (s, J = 1.8, 1 H, HC(13)). 13 C : (75.47 MHz, CDCl3) 1.4 (C(14)), 29.5 (C(6)), 39.0 (C(3)), 45.7 (C(4)), 51.7 (C(1)), 55.2 (C(11)), 114.1 (C(9)), 124.2 (C(13)), 129.6 (C(8)), 129.7 (C(12)), 130.3 (C(7)), 134.0 (C(12)), 158.4 (C(2)), 158.7 (C(10)), 206.0 (C(6)). 29 Si : (59.63 MHz, CDCl3) 27.35 TLC: Rf 0.37 (EtOAc/HexH, 1/1) [UV]
11

OMe
10 9 8 7 3 4 5 6 2 1

N

N
12

O

N

N13 OSiMe3

12d': mp: oil 1 H : (300.13 MHz, CDCl3) 0.21 (s, 9 H, H3C(13)), 2.07 (s, 3 H, H3C(6)), 2.88 (dd, J = 13.3, 7.8, 1 H, H2C(4)), 3.24 (dd, J = 13.3, 6.1, 1 H, H2C(4)), 3.71 (s, 3 H, H3C(11)), 4.55 (dd, J = 7.8, 6.1, 1 H, HC(3)), 5.03 (d, J = 5.7, 1 H, H2C(1)), 5.13 (d, J = 5.7, 1 H, H2C(1)), 6.74 (d, J = 8.6, 2 H, HC(9)), 7.00 (d, J = 8.6, 2 H, HC(8)), 7.53 (s, 2 H, HC(12)). 13 C : (75.47 MHz, CDCl3) 1.4 (C(13)), 29.5 (C(6)), 39.1 (C(3)), 45.8 (C(4)), 55.3 (C(11)), 56.7 (C(1)), 113.9 (C(9)), 129.6 (C(8)), 130.4 (C(7)), 134.3 (C(12)), 158.9 (C(2)), 160.0 (C(10)), 207.1 (C(6)). 29 Si : (59.63 MHz, CDCl3) 27.38 TLC: Rf 0.53 (EtOAc/HexH, 1/1) [UV]

34


11

OMe
10 9 8 7 3 4 5 6 2 1

N
13

N N
12

O OH

N

14d: mp: 100-102 0C 1 H : (300.13 MHz, CDCl3) 1.54 (s, 3 H, H3C(6)), 1.92 (dd, J =12.5, 13.2, 1 H, H2C(4)), 2.26 (dd, J = 6.0, 13.2, 1 H, H2C(4)), 3.53 (dd, J = 12.5, 6.0, 1 H, HC(3)), 3.84 (s, 3 H, H3C(11)), 4.76 (d, J = 12.0, 1 H, H2C(1)), 4.9 (br, 1 H, OH), 4.97 (d, J = 12.0, 1 H, H2C(1)), 6.84 (d, J = 8.6, 2 H, HC(9)), 7.06 (d, J = 8.6, 2 H, HC(8)), 7.50 (s, 1 H, HC(13)), 7.61 (s, 1 H, HC(12)). 13 C : (75.47 MHz, CDCl3) 27.0 (C(6)), 36.5 (C(3)), 40.2 (C(4)), 51.7 (C(1)), 55.3 (C(11)), 96.2 (C(5)), 114.7 (C(9)), 124.1 (C(13)), 129.4 (C(8)), 130.0 (C(7)), 133.7 (C(12)), 155.0 (C(2)), 159.1 (C(10)).
11

OMe
10 9 8 7 3 4 5 6 2 1

N
13

N N
12

O

N

OH

1

13d: H : (300.13 MHz, CDCl3) 2.07 (s, 3 H, H3C(6)), 2.85 (dd, J =12.5, 13.2, 1 H, H2C(4)), 3.33 (dd, J = 6.2, 13.2, 1 H, H2C(4)), 3.70 (s, 3 H, H3C(11)), 4.58 (dd, J = 12.5, 6.2, 1 H, HC(3)), 4.98 (d, J = 4.7, 1 H, H2C(1)), 5.08 (d, J = 4.7, 1 H, H2C(1)), 6.80 (d, J = 8.6, 2 H, HC(9)), 6.99 (d, J = 8.6, 2 H, HC(8)), 7.48 (d, J = 1.5, 1 H, HC(13)), 7.58 (d, J = 1.5, 1 H, HC(12)), 10.3 (br, 1 H, OH). 13 C : (75.47 MHz, CDCl3) 29.6 (C(6)), 38.0 (C(3)), 41.2 (C(4)), 50.2 (C(1)), 55.2 (C(11)), 114.5 (C(9)), 124.2 (C(13)), 129.0 (C(8)), 129.8 (C(12)), 130.4 (C(7)), 133.9 (C(12)), 154.2 (C(2)), 159.0 (C(10)), 206.6 (C(6)).
12 11 10 9 4 5 6 3 2 1 13

N N
15

14

7 8

O

O

N

19: 1 H : (300.13 MHz, 300K, CDCl3) 1.49 (s, 3 H, H3C(7)), 1.58 (d, J = 6.0, 3 H, H3C(1)), 2.27 (dd, J = 13.0, 8.0, 1 H, H2C(5)), 3.29 (s, 3 H, HC(4)), 4.85 (q, J = 6.0,1 H, HC(13)), 6.23 (t, J = HC(10)), 7.22 (d, J = 1.2, 1 H, HC(13)), 7.25-7.35 (m, 1 H, HC(15)).

1.94 (dd, J = 13.0, H3C(8)), 3.39 (dd, 1.2, 1 H, HC(14)), 3 H, HC(11), HC(1

12.2, 1 H, H2C(5)), J = 12.2, 8.0, 1 H, 7.02 (d, J = , 2 H, 2)), 7.48 (d, J = 1.2,

35


13

C : (75.47 MHz, 300K, CDCl3) 18.0 (C(1)), 21.2 (C(7)), 37.6 (C(4)), 39.6 (C(5)), 49.4 (C(8)), 58.4 (C(2)), 97.7 (C(6)), 105.8 (C(14)), 127.0, 127.5 and 128.4 (C(10), C(11) and C(12)), 139.1 (C(15)), 139.7 (C(9)), 159.3 (C(3)).

12 11 10 14 9 4 3

CH
13

3

5

OSi(CH3)3

15

H 3C O

7

6 8

CH

O
3

N

20: 1 H : (300.13 MHz, 300K, CDCl3) 0.12 (s, 9 H, H3C(15)), 1.33 (d, J = 5.8, 3 H, H3C(14)), 1.44 (s, 3 H, H3C(8)), 1.88 (dd, J = 13.1, 12.5, 1 H, H2C(5)), 2.29 (dd, J = 13.1, 8.1, 1 H, H2C(5)), 3.31 (s, 3 H, H3C(7)), 3.84 (dd, J = 8.1, 12.5, 1 H, HC(4)), 4.29 (q, J = 5.8,1 H, HC(13)), 7.15-7.35 (m, 5 H, HC(10), HC(11), HC(12)). 13 C : (75.47 MHz, 300K, CDCl3) -5.1 (C(15)), 15.3 and 16.3 (C(14) and C(8)), 31.2 (C(4)), 35.2 (C(5)), 44.2 (C(7)), 63.2 (C(13)), 92.0 (C(6)), 121.5, 123.4 and 123.5 (C(10), C(11) and C(12)), 135.9 (C(9)), 157.1 (C(3)). 29 Si : (59.63 MHz, 300K, CDCl3) 17.09 : C17H27NO3Si (321.49) : C, 63.51; H, 8.47; N, 4.36 % : C, 63.55; H, 8.40; N, 4.15 %

10

OMe
9 8 7 6 3 4 5 2 1 11

N
13

O 14 OSiMe3

N

N
12

12a: mp: 225-227 0C (EtOH) 1 H : (300.13 MHz, CDCl3) 0.14 (s, 9 H, H3C(15)), 1.75 (ddd, J = 3.0, 13.2, 12.5, 1 H, H2C(4)), 2.03 (ddd, J =4.1, 13.2, 7.8, 1 H, H2C(4)), 3.33 (dd, J =7.8, 12.5, 1 H, HC(3)), 3.78 (s, 3 H, H3C(10)), 4.45 (s, 2 H, H2C(1)), 5.32 (dd, J =3.0, 4.1 , 1 H, HC(5)), 6.71 (s, 1 H, HC(13)), 6.82 (d, J = 8.6, 2 H, HC(8)), 6.96 (d, J = 8.6, 2 H, HC(7)), 7.04 (s, 2 H, HC(11) and HC(12)). 13 C : (75.47 MHz, CDCl3) 1.4 (C(14)), 35.9 (C(3)), 49.0 (C(4)), 47.6 (C(1)), 55.1 (C(10)), 92.5 (C(5)), 114.7 (C(8)), 118.5 (C(13)), 129.3 (C(12)), 129.0 (C(7)), 131.1 (C(6)), 137.2 (C(11)), 155.0 (C(2)), 160.2 (C(9)). TLC: Rf 0.51 (EtOAc/HexH, 1/1) [UV]

36


10

OMe
9 8

67 3 4 5

2

1

11

N
13

O OH

N

N
12

14a: mp: oil 1 H : (300.13 MHz, DMSO-d6) 1.92 (ddd, J = 13.0, 12.1, 3.9, 1 H, H2C(4)), 2.00 (ddd, J = 13.0, 6.9, 4.2 , 1 H, H2C(4)), 3.47 (dd, J = 12.1, 6.9, 1 H, HC(3)), 3.74 (s, 3 H, H3C(10)), 4.43 (d, J = 11.4, 1 H, H2C(1)), 4.52 (d, J = 11.4, 1 H, H2C(1)) 5.32 (dd, J = 3.9, 4.2, 1 H, HC(5)), 6.84 (s, 1 H, HC(13)), 6.90 (d, J = 8.9, 2 H, HC(8)), 7.05 (d, J = 8.9, 2 H, HC(8)), 7.20 (s, 2 H, HC(11) and HC(12)). 13 C : (75.47 MHz, CDCl3) 33.4 (C(4)), 34.0 (C(3)), 48.2 (C(1)), 55.1 (C(10)), 90.4 (C(5)), 114.4 (C(8)), 119.3 (C(13)), 128.4 (C(12)), 129.3 (C(7)), 131.1 (C(6)), 137.4 (C(11)), 154.9 (C(2)), 158.4 (C(9)).
10

OMe
9 8

67 3 4 5

2

1

11

N
13

O OH

N

N
12

14a': mp: oil 1 H : (300.13 MHz, DMSO-d6) 1.78 (ddd, J = 13.0, 12.7, 3.1, 1 H, H2C(4)), 2.23 (ddd, J = 13.0, 7.2, 3.5, 1 H, H2C(4)), 3.55 (dd, J = 12.7, 7.2, 1 H, HC(3)), 3.74 (s, 3 H, H3C(10)), 4.40 (d, J = 12.1, 1 H, H2C(1)), 4.49 (d, J = 12.1, 1 H, H2C(1)) 5.12 (dd, J = 3.1, 3.5, 1 H, HC(5)), 6.84 (s, 1 H, HC(13)), 6.90 (d, J = 8.6, 2 H, HC(8)), 7.05 (d, J = 8.6, 2 H, HC(8)), 7.20 (s, 2 H, HC(11) and HC(12)). 13 C : (75.47 MHz, CDCl3) 35.9 (C(4)), 38.7 (C(3)), 47.7 (C(1)), 55.1 (C(10)), 93.8 (C(5)), 114.4 (C(8)), 119.3 (C(13)), 128.4 (C(12)), 129.3 (C(7)), 131.1 (C(6)), 137.5 (C(11)), 156.2 (C(2)), 158.4 (C(9)).

15 16, 17 ASENA (1 ) CH2Cl2 (1 ml) (1 , 0.1 ml) (0.05 , 0.06 ). 5 . . 24 . . 0.41 15 (95%). (3 ml), 3 200/ 0.08 torr. . 0.35 . 16 (97%). MeOH (5 ml) NH4F (20 mg). 24 , , EtOAc : PE = 1 : 5. 0.33 17 (91%).

37


13

OMe
12 11 10 9 2 5 7 6 4 3 1

CN
3

N O 14 OSi15 e OMe SiMe M 3
8

15: mp: oil 1 H : (300.13 MHz, CDCl3) 0.16 (s, 9 H, H3C(14)), 0.27 (s, 9 H, H3C(15)), 1.21 (s, 3 H, H3C(7)), 2.09 (dd, J = 14.0, 6.5, 1 H, H2C(5)), 2.61 (dd, J = 14.0, 7.7, 1 H, H2C(5)), 2.93 (d, J = 7.8, 1 H, H2C(2)), 3.18 (s, 3 H, H3C(8)), 3.42 (d, J = 7.8, 1 H, H2C(2)), 3.77 (s, 3 H, H3C(13)), 3.89 (dd, J = 6.5, 7.7, 1 H, HC(4)), 6.87 (d, J = 8.6, 2 H, HC(11)), 7.18 (d, J = 8.6, 2 H, HC(10)). 13 C : (75.47 MHz, CDCl3) -0.7 (C(15)), 1.9 (C(14)), 16.2 (C(2)), 25.4 (C(7)), 43.1 (C(4)), 45.1 (C(5)), 48.6 (C(8)), 55.2 (C(13)), 100.5 (C(6)), 114.4 (C(11)), 115.4 (C(1)) 128.6 (C(11)), 131.9 (C(9)), 155.0 (C(3)), 158.8 (C(12)). 29 Si : (59.63 MHz, CDCl3) 10.48 (COSi) 26.99 (NOSi) TLC: Rf 0.72 (EtOAc/HexH, 1/1) [UV]
13

OMe
12 11 10 9 2 5 7 6 4 3 1

NH

2

NO O 14 OMe SiMe 3
8

16: mp: oil 1 H : (300.13 MHz, CDCl3) 0.09 (s, 9 H, H3C(14)), 1.19 (s, 3 H, H3C(7)), 2.27 (dd, J = 13.5, 6.9, 1 H, H2C(5)), 2.51 (dd, J = 13.5, 11.2, 1 H, H2C(5)), 3.18 (s, 3 H, H3C(8)), 3.77 (s, 3 H, H3C(13)), 4.02 (dd, J = 11.2, 6.9, 1 H, HC(4)), 4.47 (s, 2 H, NH2), 4.85 (s, I H, HC(2)), 6.81 (d, J = 8.6, 2 H, HC(11)), 7.19 (d, J = 8.6, 2 H, HC(10)). 13 C : (75.47 MHz, CDCl3) 1.7 (C(14)), 26.4 (C(7)), 39.1 (C(4)), 44.2 (C(5)), 48.6 (C(8)), 55.2 (C(13)), 79.2 (C(2)), 100.6 (C(6)), 114.0 (C(11)), 128.8 (C(10)), 135.3 (C(9)), 158.8 (C(12)), 168.2 and 169.1 (C(1) and C(3)). 29 Si : (59.63 MHz, CDCl3) 10.58 TLC: Rf 0.56 (EtOAc/HexH, 1/1) [UV]

38


OMe
11 10 9 8 5 7 6 4 3 2 1

12

NH

2

O

NO

17: mp: 87-910C 1 H : (300.13 MHz, CDCl3) 2.11 (s, 3 H, H3C(7)), 2.84 (dd, J = 13.0, 6.6, 1 H, H2C(5)), 3.35 (dd, J = 13.0, 7.9, 1 H, H2C(5)), 3.72 (s, 3 H, H3C(12)), 4.39 (dd, J = 6.6, 7.9, 1 H, HC(4)), 4.53 (s, 2 H, NH2), 4.78 (s, I H, HC(2)), 6.81 (d, J =8.6 , 2 H, HC(10)), 7.19 (d, J = 8.6, 2 H, HC(9)). 13 C : (75.47 MHz, CDCl3) 30.4 (C(7)), 38.4 (C(4)), 47.7 (C(5)), 55.2 (C(12)), 79.7 (C(2)), 114.1 (C(10)), 128.8 (C(9)), 133.5 (C(8)), 158.5 (C(11)), 167.1 and 168.6 (C(1) and C(3)), 206.9 (C(4)). TLC: Rf 0.37 (EtOAc/HexH, 1/1) [UV]

ASENA 5d c 1-. TMSCl (5.5 , 0.81 ) N- (6 , 0.43 ) H2Cl2 (10 ) 1 . 0.5M ASENA H2Cl2 (8 ) 00. 12 . NaHCO3 (. -) (10 )/ EtOAc (50 ). 2 Brine (10 ). Na2SO4. . 1.35 g (91%) 19.
11 10 9 8 4 5 6 3 2 1

Cl

N 13 O 12 OSiMe 3 OMe SiMe 3
7

21: mp: oil 1 H : (300.13 MHz, CDCl3) 0.12 (s, 9 H, H3C(13)), 0.23 (s, 9 H, H3C(14)), 1.32 (s, 3 H, H3C(6)), 2.50 (d, J = 6.1, 2 H, H2C(5)), 3.25 (s, 3 H, H3C(7)), 4.08 (d, J = 7.5, 1 H, H2C(1)), 4.16 (d, J = 7.5, 1 H, H2C(1)), 4.73 (t, J = 6.1, 1 H, H3C(3)), 7.18 - 7.45 (m, 5 H, HC(9), HC(10) and HC(11)). 13 C : (75.47 MHz, CDCl3) -0.8 (C(13)), 1.7 (C(12)), 25.9 (C(6)), 39.7 (C(3)), 41.5 (C(4)), 43.5 (C(1)), 48.6 (C(7)), 100.7 (C(5)), 126.5, 128.2 and 128.7 (C(9), C(10) and C(11)), 140.7 (C(8)), 161.7 (C(2)). 29 Si : (59.63 MHz, CDCl3) 10.45 (COSi) 26.08 (NOSi) TLC: Rf 0.79 (EtOAc/HexH, 1/1) [UV]

ASENA, TMSOTf. (1 , 0.14 g) (0.1 , 20 ) H2Cl2 (2 ) - 780 10 . ASENA 2 H2Cl2. - 30 0. 18 . NaHCO3 (. -) (10 )/ EtOAc (15 ). 2 Brine (5 ). Na2SO4. . 0.08 g (30%) 22 0.04 g (18%) 23.

39


, -780 24 23 46%.
12 11 10 9 5 6 7 8 4 3 13

N
14

N
15

16

O

N

22: mp: 74-77 (EtOAc/PE = 1/1) 1 H : (300.13 MHz, CDCl3) 1.22 and 1.35 (2s, 6 H, H3C(7) and H3C(8)), 1.90 (dd, J = 13.2, 11.8, 1 H, H2C(5)), 2.04 (dd, J = 13.2, 8.1, 1 H, H2C(5)), 3.24 (dd, J = 8.1, 11.8, 1 H, HC(4)), 4.60 and 4.68 (2d, J = 14.0, 2 H, H2C(13)), 6.20 (dd, J = 1.8, 2.2, 1 H, HC(15)), 7.12 - 7.30 (m, 6 H, HC(10), HC(11), HC(12), HC(14)), 7.51 (d, J = 2.2, HC(16)). 13 C : (75.47 MHz, CDCl3) 22.6 and 28.3 (C(7) and C(8)), 37.8 (C(4)), 40.8 (C(5)), 53.8 (C(13)), 75.0 (C(6)), 105.7 (C(15)), 127.4, 128.4 and 129.1 (C(10), C(11), C(12)), 129.8 (C(14)), 139.6 (C(9)), 139.9 (C(16)), 155.0 (C(3)). TLC: Rf 0.42 (hexane/EtOAc, 1/1) [UV]
12 11 10 9 5 6 7 8 4 3 13

OH

O

N

23: mp: oil 1 H : (300.13 MHz, CDCl3) 1.27 and 1.34 (2s, 6 H, H3C(7) and H3C(8)), 1.90 (dd, J = 14.0, 11.8, 1 H, H2C(5)), 2.05 (dd, J = 14.0, 8.1, 1 H, H2C(5)), 2.7 (br, 1 H, OH), 3.51 (dd, J = 8.1, 11.8, 1 H, HC(4)), 3.90 (s, 2 H, H2C(13)), 7.12 - 7.30 (m, 5 H, HC(10), HC(11), HC(12)). 13 C : (75.47 MHz, CDCl3) 22.8 and 28.4 (C(7) and C(8)), 37.6 (C(4)), 40.4 (C(5)), 62.3 (C(13)), 74.8 (C(6)), 127.4, 128.2 and 129.0 (C(10), C(11), C(12)), 139.5 (C(9)), 156.9 (C(3)). TLC: Rf 0.26 (hexane/EtOAc, 1/1) [UV]

ASENA 5e c TMSBr. TMSBr (5.5 , 0.73 ) (0.5 , 0.07 ) N (10 ) 1 . 0.5 M ASENA H2Cl2 (8 ) - 300. 12 . NaHCO3 (. -) (10 )/ EtOAc (50 ). 2 Brine (10 ). Na2SO4. . 0.59 g (42%) 19.
12 11 10 9 5 6 7 8 4 3 13

Br

O

N

40


19: mp: 97-990 (PE) 1 H : (300.13 MHz, CDCl3) 1.34 and 1.39 (2s, 6 H, H3C(7) and H3C(8)), 1.98 (dd, J = 13.5, 12.5, 1 H, H2C(5)), 2.13 (dd, J = 13.5, 8.1, 1 H, H2C(5)), 3.65 (d, J = 10.3, 1 H, H2C(13)), 3.87 (dd, J = 8.1, 12.5, 1 H, HC(4)), 4.03 (d, J = 10.3, 1 H, H2C(13)), 7.17 - 7.41 (m, 5 H, HC(10), HC(11), HC(12)). 13 C : (75.47 MHz, CDCl3) 23.1 and 28.3 (C(7) and C(8)), 31.7 (C(13)), 37.0 (C(4)), 40.2 (C(5)), 75.6 (C(6)), 127.6, 128.3 and 129.2 (C(10), C(11), C(12)), 139.2 (C(9)), 155.4 (C(3)). TLC: Rf 0.79 (hexane/EtOAc, 1/1) [UV]

41


5d 3d. 1. 5d.

42


1. [Е] [њ] 5d. ______________________________________________________________________ Si(2)-O(2) 1.6825(14) O(4)-C(11) 1.375(2) Si(2)-C(2C) Si(2)-C(2A) Si(2)-C(2B) O(1)-C(6) O(1)-N(2) N(2)-O(2) N(2)-C(3) O(3)-C(6) O(3)-C(18) C(3)-C(7) C(3)-C(4) O(2)-Si(2)-C(2C) O(2)-Si(2)-C(2A) C(2C)-Si(2)-C(2A) O(2)-Si(2)-C(2B) C(2C)-Si(2)-C(2B) C(2A)-Si(2)-C(2B) C(6)-O(1)-N(2) O(2)-N(2)-C(3) O(2)-N(2)-O(1) C(3)-N(2)-O(1) N(2)-O(2)-Si(2) C(6)-O(3)-C(18) C(7)-C(3)-N(2) C(7)-C(3)-C(4) N(2)-C(3)-C(4) C(11)-O(4)-C(19) C(8)-C(4)-C(3) C(8)-C(4)-C(5) 1.844(2) 1.847(2) 1.848(2) 1.430(2) 1.4806(19) 1.4128(19) 1.442(2) 1.404(2) 1.420(3) 1.318(3) 1.517(2) 111.64(9) 109.31(10) 109.61(12) 101.38(9) 112.47(11) 112.19(11) 112.43(13) 109.85(13) 99.03(12) 108.44(13) 113.85(10) 116.71(16) 122.41(17) 126.63(17) 110.62(14) 116.65(16) 113.03(15) 113.39(15) O(4)-C(19) C(4)-C(8) C(4)-C(5) C(5)-C(6) C(6)-C(17) C(8)-C(9) C(8)-C(13) C(9)-C(10) C(10)-C(11) C(11)-C(12) C(12)-C(13) C(3)-C(4)-C(5) C(6)-C(5)-C(4) O(3)-C(6)-O(1) O(3)-C(6)-C(17) O(1)-C(6)-C(17) O(3)-C(6)-C(5) O(1)-C(6)-C(5) C(17)-C(6)-C(5) C(9)-C(8)-C(13) C(9)-C(8)-C(4) C(13)-C(8)-C(4) C(8)-C(9)-C(10) C(11)-C(10)-C(9) O(4)-C(11)-C(10) O(4)-C(11)-C(12) C(10)-C(11)-C(12) C(13)-C(12)-C(11) C(12)-C(13)-C(8) 1.422(3) 1.513(3) 1.532(3) 1.516(3) 1.515(3) 1.381(3) 1.389(3) 1.390(3) 1.377(3) 1.383(3) 1.382(3) 108.09(15) 110.65(15) 111.55(15) 113.39(16) 103.10(15) 105.51(15) 109.88(15) 113.52(17) 117.49(18) 121.65(17) 120.82(16) 122.09(18) 119.09(18) 124.07(18) 115.83(17) 120.10(18) 119.88(18) 121.33(17)

______________________________________________________________________

43


2. [њ] 5d. _______________________________________________________________________ C(6)-O(1)-N(2)-O(2) 177.37(13) N(2)-O(1)-C(6)-C(17) -179.87(14) C(6)-O(1)-N(2)-C(3) C(3)-N(2)-O(2)-Si(2) O(1)-N(2)-O(2)-Si(2) C(2C)-Si(2)-O(2)-N(2) C(2A)-Si(2)-O(2)-N(2) C(2B)-Si(2)-O(2)-N(2) O(2)-N(2)-C(3)-C(7) O(1)-N(2)-C(3)-C(7) O(2)-N(2)-C(3)-C(4) O(1)-N(2)-C(3)-C(4) C(7)-C(3)-C(4)-C(8) N(2)-C(3)-C(4)-C(8) C(7)-C(3)-C(4)-C(5) N(2)-C(3)-C(4)-C(5) C(8)-C(4)-C(5)-C(6) C(3)-C(4)-C(5)-C(6) C(18)-O(3)-C(6)-O(1) C(18)-O(3)-C(6)-C(17) C(18)-O(3)-C(6)-C(5) N(2)-O(1)-C(6)-O(3) 62.82(17) -119.31(12) 127.23(10) -48.50(14) 72.93(14) -168.46(12) 16.9(2) 124.14(18) -169.38(13) -62.14(17) -1.1(3) -174.54(14) -127.5(2) 59.11(18) 179.84(15) -54.02(19) 59.0(2) -56.9(2) 178.30(17) 58.11(18) N(2)-O(1)-C(6)-C(5) C(4)-C(5)-C(6)-O(3) C(4)-C(5)-C(6)-O(1) C(4)-C(5)-C(6)-C(17) C(3)-C(4)-C(8)-C(9) C(5)-C(4)-C(8)-C(9) C(3)-C(4)-C(8)-C(13) C(5)-C(4)-C(8)-C(13) C(13)-C(8)-C(9)-C(10) C(4)-C(8)-C(9)-C(10) C(8)-C(9)-C(10)-C(11) C(19)-O(4)-C(11)-C(10) -58.54(18) -65.78(18) 54.6(2) 169.45(16) -70.1(2) 53.4(2) 107.82(19) -128.71(18) -1.0(3) 176.94(17) 0.0(3) 4.2(3)

C(19)-O(4)-C(11)-C(12) -176.07(19) C(9)-C(10)-C(11)-O(4) -179.49(18) C(9)-C(10)-C(11)-C(12) 0.8(3)

O(4)-C(11)-C(12)-C(13) 179.80(17) C(10)-C(11)-C(12)-C(13) C(11)-C(12)-C(13)-C(8) C(9)-C(8)-C(13)-C(12) -0.5(3) -0.6(3) 1.4(3)

C(4)-C(8)-C(13)-C(12) -176.62(17)

_______________________________________________________________________

44


2. 3d.

45


3. [Е] [њ] 3d. ______________________________________________________________________ O(1)-N(2) O(1)-C(6) O(2)-N(2) N(2)-C(3) O(3)-C(6) O(3)-C(15) C(3)-C(7) C(3)-C(4) O(4)-C(11) O(4)-C(16) 1.429(3) 1.457(3) 1.268(3) 1.302(3) 1.408(3) 1.442(3) 1.492(4) 1.503(3) 1.374(3) 1.426(4) C(4)-C(5) C(4)-C(8) C(5)-C(6) C(6)-C(14) C(8)-C(13) C(8)-C(9) C(9)-C(10) C(10)-C(11) C(11)-C(12) C(12)-C(13) O(1)-C(6)-C(14) N(2)-O(1)-C(6) O(2)-N(2)-C(3) O(2)-N(2)-O(1) C(3)-N(2)-O(1) C(6)-O(3)-C(15) N(2)-C(3)-C(7) N(2)-C(3)-C(4) C(7)-C(3)-C(4) C(11)-O(4)-C(16) C(3)-C(4)-C(5) C(3)-C(4)-C(8) C(5)-C(4)-C(8) C(6)-C(5)-C(4) O(3)-C(6)-O(1) 114.86(17) 127.3(2) 111.17(18) 121.5(2) 114.9(2) 116.6(2) 123.2(2) 120.1(2) 117.2(2) 112.3(2) 111.2(2) 111.0(2) 111.7(2) 109.76(19) C(5)-C(6)-C(14) C(13)-C(8)-C(9) C(13)-C(8)-C(4) C(9)-C(8)-C(4) C(10)-C(9)-C(8) C(9)-C(10)-C(11) O(4)-C(11)-C(10) O(4)-C(11)-C(12) C(10)-C(11)-C(12) C(13)-C(12)-C(11) C(8)-C(13)-C(12) 1.532(4) 1.533(4) 1.510(4) 1.512(4) 1.383(3) 1.411(3) 1.377(4) 1.391(4) 1.394(4) 1.391(4) 103.40(19) 113.8(2) 117.4(2) 122.1(2) 120.4(2) 120.7(2) 120.9(2) 116.3(2) 124.4(2) 119.3(2) 119.1(2) 122.4(2)

O(3)-C(6)-C(5) O(1)-C(6)-C(5) O(3)-C(6)-C(14)

107.6(2) 107.9(2) 114.2(2) 46


4. [њ] 3d. _____________________________________ C(6)-O(1)-N(2)-O(2) -153.34(19) C(6)-O(1)-N(2)-C(3) 27.9(3) O(2)-N(2)-C(3)-C(7) 2.7(4) O(1)-N(2)-C(3)-C(7) -178.7(2) O(2)-N(2)-C(3)-C(4) 178.7(2) O(1)-N(2)-C(3)-C(4) -2.7(3) N(2)-C(3)-C(4)-C(5) 7.2(3) C(7)-C(3)-C(4)-C(5) -176.9(2) N(2)-C(3)-C(4)-C(8) 132.3(2) C(7)-C(3)-C(4)-C(8) -51.8(3) C(3)-C(4)-C(5)-C(6) -35.4(3) C(8)-C(4)-C(5)-C(6) -160.5(2) C(15)-O(3)-C(6)-O(1) 60.9(3) C(15)-O(3)-C(6)-C(5) 178.0(2) C(15)-O(3)-C(6)-C(14) -54.7(3) N(2)-O(1)-C(6)-O(3) 62.1(2) N(2)-O(1)-C(6)-C(5) -54.8(2) N(2)-O(1)-C(6)-C(14) -175.64(19) C(4)-C(5)-C(6)-O(3) -59.8(3) C(4)-C(5)-C(6)-O(1) 58.5(3) C(4)-C(5)-C(6)-C(14) 172.6(2) C(3)-C(4)-C(8)-C(13) 121.7(2) C(5)-C(4)-C(8)-C(13) -112.5(3) C(3)-C(4)-C(8)-C(9) -60.5(3) C(5)-C(4)-C(8)-C(9) 65.2(3) C(13)-C(8)-C(9)-C(10) 1.7(4) C(4)-C(8)-C(9)-C(10) -176.2(2) C(8)-C(9)-C(10)-C(11) 0.4(4) C(16)-O(4)-C(11)-C(10) -177.2(3) C(16)-O(4)-C(11)-C(12) 3.2(4) C(9)-C(10)-C(11)-O(4) 178.5(2) C(9)-C(10)-C(11)-C(12) -1.8(4) O(4)-C(11)-C(12)-C(13) -179.3(2) C(10)-C(11)-C(12)-C(13) 1.0(4) C(9)-C(8)-C(13)-C(12) -2.5(4) C(4)-C(8)-C(13)-C(12) 175.3(2) C(11)-C(12)-C(13)-C(8) 1.1(4) ____________________________________


48