Acid-catalyzed rearrangement of epoxy alcohol derivatives having the electron-withdrawing protective groups (acyl or sulfonyl): Asymmetric synthesis of chiral quaternary carbon and spiro centers and its application to natural products synthesis

被引：10

作者：

Fujioka, H ^{[1
]}

Yoshida, Y ^{[1
]}

Kita, Y ^{[1
]}

机构：

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

来源：

JOURNAL OF SYNTHETIC ORGANIC CHEMISTRY JAPAN | 2003年 / 61卷 / 02期

关键词：

rearrangement; epoxy acylate; epoxy sulfonate; asymmetric synthesis; chiral quaternary carbon; chiral spiro center; fredericamycin A; (+)-(S)-sporochnol A; (-)-aphanorphine; (-)-alpha-herbertenol;

D O I：

10.5059/yukigoseikyokaishi.61.133

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Rearrangements of 1, 2-epoxy alcohol derivatives having electron-withdrawing protective groups such as acyl or sulfonyl group have been developed leading to the asymmetric construction of chiral quaternary carbon centers and spiro centers. The success of the novel rearrangements here depends on the electron-withdrawing property of the protective groups. The methods were applied to the asymmetric syntheses of several natural products such as fredericamycin A, (+)-(S)-sporochnol A, (-)-aphanorphine, and (-)-alpha-herbertenol.

引用

页码：133 / 143

页数：11

共 51 条

[1]

ABAD A, 1993, SYNLETT, P895

[2] LEWIS ACID-CATALYZED REARRANGEMENTS OF STRUCTURALLY RELATED ALPHA,BETA-UNSATURATED EPOXY KETONES AND OXIMES - A COMPLEMENTARY APPROACH TO THE SYNTHESIS OF ISOMERIC 1,4-DIKETOSPIRO[NORMAL,META] ALKANES [J].

BACH, RD ;

TUBERGEN, MW ;

KLIX, RC .

TETRAHEDRON LETTERS, 1986, 27 (31) :3565-3568

[3] CONCERTED 1,2-CARBONYL MIGRATIONS IN ORGANIC-SYNTHESIS - A PRACTICAL SYNTHESIS OF SPIRO CYCLIC 1,3-DIKETONES [J].

BACH, RD ;

KLIX, RC .

JOURNAL OF ORGANIC CHEMISTRY, 1985, 50 (25) :5438-5440

[4] The semi-pinacol rearrangement of homochiral epoxyalcohols catalysed by rare earth triflates [J].

Bickley, JF ;

Hauer, B ;

Pena, PCA ;

Roberts, SM ;

Skidmore, J .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 2001, (11) :1253-1255

[5] A STABLE AND EASILY PREPARED CATALYST FOR THE ENANTIOSELECTIVE REDUCTION OF KETONES - APPLICATIONS TO MULTISTEP SYNTHESES [J].

COREY, EJ ;

BAKSHI, RK ;

SHIBATA, S ;

CHEN, CP ;

SINGH, VK .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (25) :7925-7926

[6] Stereocontrolled rearrangement of silylated vinyloxiranes into alpha-trialkylsilyl-beta,gamma,-unsaturated aldehydes. [J].

Courillon, C ;

LeFol, R ;

Vandendris, E ;

Malacria, M .

TETRAHEDRON LETTERS, 1997, 38 (31) :5493-5496

[7]

FINN MG, 1985, ASYMMETRIC SYNTHESIS, V5, pCH8

[8] ASYMMETRIC-SYNTHESIS OF CHIRAL SPIROCYCLANES - SELECTIVE FORMATION OF 2-ACYLOXY-1-OXOSPIRO[4.N]ALKANES BY REGIOSELECTIVE AND STEREOSELECTIVE REARRANGEMENT OF ALPHA,BETA-EPOXY ACYLATES IN BICYCLO[N.3.0]ALKANE SYSTEMS [J].

FUJIOKA, H ;

KITAGAKI, S ;

IMAI, R ;

KONDO, M ;

OKAMOTO, S ;

YOSHIDA, Y ;

AKAI, S ;

KITA, Y .

TETRAHEDRON LETTERS, 1995, 36 (18) :3219-3222

[9] THE REARRANGEMENT OF ALPHA,BETA-EPOXY KETONES .2. MIGRATORY APTITUDES [J].

HOUSE, HO ;

REIF, DJ .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1955, 77 (24) :6525-6532

[10] Stereospecific rearrangements of optically active 2-aryl-3-ethenyloxiranes to give optically active beta-ethenylbenzeneethanols: Benzyl vs. allyl cations and an efficient synthesis of (S)-ibuprofen [J].

Jung, ME ;

Anderson, KL .

TETRAHEDRON LETTERS, 1997, 38 (15) :2605-2608

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