N - 43 1--4- 44 , 45 .( 15) [17] , .
15.
- [18], ( 16). (46) - 2--3- , 47, , 48. 49.
16.
50 , .[19]
17.
, 51. , .
.
, , , . . [20] 52 53 ( 18). 54, 55 .
18.
, [21], Boc- 56 57, - 58, . 59 ( 19) , Boc- .
19.
, .
3 2-(1 H --3-) () 4 1,4,5,6- 5, (. 1). -, , .
, in situ . 4-, () .
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|
α-β 60 - 61 62. ( 20)
20
, (1,75 ) (10 ). , . , (12 ) 4 .
α-β 60 . . 63 .
22
. , , , α- β- ( 23)
23
, 4- 64, 2- (4 0,6 ) 16 . , . , . 1H. , 5- .. , .
(4 0.6 , 16 ) . , . 1H , , . (8 0.6 ) . . , , , 65 66, .
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1H , , . COSY , (4.2 ..) (8.7 ..), , . , , ( 1).
1.
R | 65 | 66 |
H | 61% | 5% |
Me | 68% | 9% |
F | 50% | 19% |
1 13 Brüker AC-200 (200.13 50.3 ), Bruker AC-300 (300 75.5 ) Bruker DRX-500 (500 125.3 ) CDCl3, (CD3)2SO, 0.05% Me4Si ; COSY, NOESY HMBC Bruker AVANCE II 300 Bruker DRX-500. - Finnigan MAT INCOS-50 (, 70 , ) Finnigan LCQ (ESI). Silicagel 60 (Merck). ( 60, 0.0400.063 , Merck) , ~1: 100. .
3.1. α-β .
, 50 10% NaOH (120 ) 1 (10) 2 (40). 3 , 3 . . 5 / 3:1.
4- -3--2-: -81%. 1H (CDCl3): δ = 2.17 (c, 3H), 6.30 (, J = 12 , 1H,), 7.09 (, J = 12 , 1H), 7.387.90 (, 5H).
4-(4-) -3- -2-: -85%. 1H (CDCl3): δ 7.89 (, 2H), 7.58 (, 3H), 6.69 (, 1H), 2.37 (, J =16.0 , 6H).
4-(4-)-3- -2-: -67% 1H (CDCl3): δ 7.56 7.46 (, 3H), 7.10 (, J = 8.5 , 2H), 6.65 (, J = 16.3 , 1H), 2.38 (, 3H).