Application of the combined C-H activation/Cope rearrangement as a key step in the total syntheses of the assigned structure of (+)-elisabethadione and a (+) p-benzoquinone natural product

被引：25

作者：

Davies, Huw M. L. ^{[1
]}

Dai, Xing ^{[1
]}

机构：

[1] SUNY Buffalo, Dept Chem, Buffalo, NY 14260 USA

来源：

TETRAHEDRON | 2006年 / 62卷 / 45期

基金：

美国国家科学基金会;

关键词：

combined C-H activation/Cope rearrangement; total synthesis; (+)-elisabethadione (3); rhodium carbenoid; C-H insertion;

D O I：

10.1016/j.tet.2006.05.086

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The enantioselective total syntheses of the assigned structure of (+)-elisabethadione (3) and the (+)-p-benzoquinone natural product 4 is described. The stereocontrolled formation of the three key stereocenters in the natural products is achieved in a single step through the combined C-H activation/Cope rearrangement, a C-H functionalization process catalyzed by the dirhodium tetraprolinate, Rh-2(R-DOSP)4 (DOSP=(N-dodecylbenzenesulfonyl)prolinate). (c) 2006 Published by Elsevier Ltd.

引用

收藏

页码：10477 / 10484

页数：8

相关论文

共 48 条

[1] Identification of anti-inflammatory diterpenes from the marine gorgonian Pseudopterogorgia elisabethae [J].

Ata, A ;

Kerr, RG ;

Moya, CE ;

Jacobs, RS .

TETRAHEDRON, 2003, 59 (23) :4215-4222

[2] Elisabethamine:: a new diterpene alkaloid from Pseudopterogorgia elisabethae [J].

Ata, A ;

Kerr, RG .

TETRAHEDRON LETTERS, 2000, 41 (31) :5821-5825

[3] Efficient total syntheses of (-)-colombiasin A and (-)-elisapterosin B: Application of the Cr-catalyzed asymmetric quinone Diels-Alder reaction [J].

Boezio, AA ;

Jarvo, ER ;

Lawrence, BM ;

Jacobsen, EN .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2005, 44 (37) :6046-6050

[4]

Cesati RR, 2004, J AM CHEM SOC, V126, P96

[5] First enantiospecific total synthesis of the antitubercular marine natural product pseudopteroxazole. Revision of assigned stereochemistry [J].

Davidson, JP ;

Corey, EJ .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (44) :13486-13489

[6] Intermolecular C-H insertions of donor/acceptor-substituted rhodium carbenoids: A practical solution for catalytic enantioselective C-H activation [J].

Davies, HML ;

Loe, O .

SYNTHESIS-STUTTGART, 2004, (16) :2595-2608

[7] Catalytic enantioselective C-H activation by means of metal-carbenoid-induced C-H insertion [J].

Davies, HML ;

Beckwith, REJ .

CHEMICAL REVIEWS, 2003, 103 (08) :2861-2903

[8] Combined C-H activation/cope rearrangement as a strategic reaction in organic synthesis: Total synthesis of (-)-colombiasin A and (-)-elisapterosin B [J].

Davies, HML ;

Dal, X ;

Long, MS .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (07) :2485-2490

[9] Asymmetric C-H insertion of Rh(II) stabilized carbenoids into acetals: A C-H activation protocol as a Claisen condensation equivalent [J].

Davies, HML ;

Yang, J ;

Nikolai, J .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 2005, 690 (24-25) :6111-6124

[10] Direct synthesis of (+)-erogorgiaene through a kinetic enantiodifferentiating step [J].

Davies, HML ;

Walji, AM .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2005, 44 (11) :1733-1735

← 1 2 3 4 5 →