A practical and efficient synthesis of the C-16-C-28 spiroketal fragment (CD) of the spongistatins

被引：47

作者：

Gaunt, MJ ^{[1
]}

Hook, DF ^{[1
]}

Tanner, HR ^{[1
]}

Ley, SV ^{[1
]}

机构：

[1] Univ Cambridge, Dept Chem, Cambridge CB2 1EW, England

来源：

ORGANIC LETTERS | 2003年 / 5卷 / 25期

关键词：

D O I：

10.1021/ol035848h

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

[GRAPHICS] A practical and efficient route to the CD spiroketal (C-16-C-28) of the spongistatins is reported. Two stereocenters are introduced from chiral building blocks with the remainder introduced by substrate-controlled transformations. The key beta-keto-1,3-dithiane intermediate is generated by a dithiol conjugate addition to an ynone and the 1,3-dithiane unit in the C-ring plays a key role in the spiroketalization and subsequent epimerization. The synthesis requires 24 steps, with a longest linear sequence of 19 steps in an overall yield of 14.5% (for the longest linear sequence).

引用

收藏

页码：4815 / 4818

页数：4

相关论文

共 49 条

[11] Enantioselective synthesis of altohyrtin C (spongistatin 2):: Synthesis of the EF-bis(pyran) subunit [J].

Evans, DA ;

Trotter, BW ;

Côté, B ;

Coleman, PJ .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 1997, 36 (24) :2741-2744

[12] Enantioselective synthesis of altohyrtin C (spongistatin 2): Synthesis of the AB- and CD-spiroketal subunits [J].

Evans, DA ;

Coleman, PJ ;

Dias, LC .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 1997, 36 (24) :2738-2741

[13]

Fernandez-Megia E, 1998, SYNLETT, P991

[14] BIOACTIVE MARINE METABOLITES .48. CINACHYROLIDE-A - A POTENT CYTOTOXIC MACROLIDE POSSESSING 2 SPIRO KETALS FROM MARINE SPONGE CINACHYRA SP [J].

FUSETANI, N ;

SHIMODA, K ;

MATSUNAGA, S .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1993, 115 (10) :3977-3981

[15] Development of β-keto 1,3-dithianes as versatile intermediates for organic synthesis [J].

Gaunt, MJ ;

Sneddon, HF ;

Hewitt, PR ;

Orsini, P ;

Hook, DF ;

Ley, SV .

ORGANIC & BIOMOLECULAR CHEMISTRY, 2003, 1 (01) :15-16

[16] Synthesis of the C-1-C-28 ABCD unit of spongistatin 1 [J].

Gaunt, MJ ;

Jessiman, AS ;

Orsini, P ;

Tanner, HR ;

Hook, DF ;

Ley, SV .

ORGANIC LETTERS, 2003, 5 (25) :4819-4822

[17] LANTHANOIDS IN ORGANIC-SYNTHESIS .6. THE REDUCTION OF ALPHA-ENONES BY SODIUM-BOROHYDRIDE IN THE PRESENCE OF LANTHANOID CHLORIDES - SYNTHETIC AND MECHANISTIC ASPECTS [J].

GEMAL, AL ;

LUCHE, JL .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1981, 103 (18) :5454-5459

[18]

Guo JS, 1998, ANGEW CHEM INT EDIT, V37, P187, DOI 10.1002/(SICI)1521-3773(19980202)37:1/2<187::AID-ANIE187>3.0.CO

[19]

2-D

[20]

Hayward MM, 1998, ANGEW CHEM INT EDIT, V37, P192

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