Enantiodivergent preparation of optically active oxindoles having a stereogenic quaternary carbon center at the C3 position via the lipase-catalyzed desymmetrization protocol: Effective use of 2-furoates for either enzymatic esterification or hydrolysis

被引：56

作者：

Akai, S ^{[1
]}

Tsujino, T ^{[1
]}

Akiyama, E ^{[1
]}

Tanimoto, K ^{[1
]}

Naka, T ^{[1
]}

Kita, Y ^{[1
]}

机构：

[1] Osaka Univ, Grad Sch Pharmaceut Sci, Suita, Osaka 5650871, Japan

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2004年 / 69卷 / 07期

关键词：

D O I：

10.1021/jo035749h

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Both enantiomers of oxindoles 2a-h, having a stereogenic quaternary carbon center at the C3 position and a different N-protective group, were readily prepared by the lipase-catalyzed desymmetrization protocol. Thus, the transesterification of the prochiral diols 3a-h with 1-ethoxy-vinyl 2-furoate 5 was catalyzed by Candida rugosa lipase to give (R)-(+)-2a-h (68-99% ee), in which the use of a mixed solvent, (i)Pr(2)O (diisopropyl ether)-THF, was crucial. The same lipase also effected the enantioselective hydrolysis of the difuroates 4a-h in a mixture of (i)Pr(2)O, THF, and H(2)O to provide the enantiomers (S)-(-)-2a-h (82-99% ee). The products 2 obtained by both methods were stable against racemization. These enzymatic desymmetrization reactions were also applicable for other typical symmetrical difuroates 12b and 15b to provide the racemization-resistant products 13b and 16b.

引用

页码：2478 / 2486

页数：9

共 50 条

[1] Efficient lipase-catalyzed enantioselective desymmetrization of prochiral 2,2-disubstituted 1,3-propanediols and meso 1,2-diols using 1-ethoxyvinyl 2-furoate
Akai, S
Naka, T
Fujita, T
Takeba, Y
Tsujino, T
Kita, Y
[J]. JOURNAL OF ORGANIC CHEMISTRY, 2002, 67 (02) : 411 - 419
[2] Enantiodivergent synthesis of either enantiomer of ABCDE-ring analogue of antitumor antibiotic fredericamycin A via intramolecular [4+2] cycloaddition approach
Akai, S
Tsujino, T
Fukuda, N
Iio, K
Takeda, Y
Kawaguchi, KI
Naka, T
Higuchi, K
Kita, Y
[J]. ORGANIC LETTERS, 2001, 3 (25) : 4015 - 4018
[3] 1-Ethoxyvinyl 2-furoate, an efficient acyl donor for the lipase-catalyzed enantioselective desymmetrization of prochiral 2,2-disubstituted propane-1,3-diols and meso-1,2-diols
Akai, S
Naka, T
Fujita, T
Takebe, Y
Kita, Y
[J]. CHEMICAL COMMUNICATIONS, 2000, (16) : 1461 - 1462
[4] Lipase-catalyzed enantioselective desymmetrization of prochiral 3,3-bis(hydroxymethyl)oxindoles
Akai, S
Tsujino, T
Naka, T
Tanimoto, K
Kita, Y
[J]. TETRAHEDRON LETTERS, 2001, 42 (41) : 7315 - 7317
[5] Catalytic asymmetric synthesis of quaternary carbon centers.: Exploratory studies of intramolecular Heck reactions of (Z)-α,β-unsaturated anilides and mechanistic investigations of asymmetric Heck reactions proceeding via neutral intermediates
Ashimori, A
Bachand, B
Calter, MA
Govek, SP
Overman, LE
Poon, DJ
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (26) : 6488 - 6499
[6] Catalytic asymmetric synthesis of quaternary carbon centers.: Exploratory investigations of intramolecular Heck reactions of (E)-α,β-Unsaturated 2-haloanilides and analogues to form enantioenriched spirocyclic products
Ashimori, A
Bachand, B
Overman, LE
Poon, DJ
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (26) : 6477 - 6487
[7] Total synthesis of spirotryprostatin B via asymmetric nitroolefination
Bagul, TD
Lakshmaiah, G
Kawabata, T
Fuji, K
[J]. ORGANIC LETTERS, 2002, 4 (02) : 249 - 251
[8] SUBSTITUTED OXINDOLES .I. PREPARATION AND SPECTRAL CHARACTERISTICS OF SOME SIMPLE OXINDOLE DERIVATIVES
BECKETT, AH
DAISLEY, RW
WALKER, J
[J]. TETRAHEDRON, 1968, 24 (19) : 6093 - &
[9] Bódai V, 1999, SYNLETT, P759
[10] HETEROCYCLIC AROMATIC ANIONS WITH 4N+2-PI-ELECTRONS
BORDWELL, FG
FRIED, HE
[J]. JOURNAL OF ORGANIC CHEMISTRY, 1991, 56 (13) : 4218 - 4223

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