Chiral N-heterocyclic carbenes in natural product synthesis: Application of Ru-catalyzed asymmetric ring-opening/cross-metathesis and Cu-catalyzed allylic alkylation to total synthesis of baconipyrone C

被引：131

作者：

Gillingham, Dennis G. ^{[1
]}

Hoveyda, Amir H. ^{[1
]}

机构：

[1] Boston Coll, Merkert Chem Ctr, Dept Chem, Chestnut Hill, MA 02167 USA

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2007年 / 46卷 / 21期

关键词：

allylic alkylation; asymmetric catalysis; natural products; N-heterocyclic carbenes; olefin metathesis;

D O I：

10.1002/anie.200700501

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

(Chemical Equation Presented) Chiral carbenes as major players: Two recently discovered chiral N-heterocyclic carbene (NHC) complexes play a crucial role in a concise enantioselective total synthesis of baconipyrone C (see scheme). An (NHC)Cu complex catalyzes a double asymmetric allylic alkylation (AAA), and an (NHC)Ru complex catalyzes an asymmetric ring-opening/cross- metathesis (AROM/CM) to establish the absolute configuration of the target. RCM = ring-closing metathesis. © 2007 Wiley-VCH Verlag GmbH & Co. KGaA.

引用

页码：3860 / 3864

页数：5

共 46 条

[1]

[Anonymous], ANGEW CHEM

[2] MILD CONDITIONS FOR CYCLIZATION OF BETA-TRIKETIDES TO THE CORRESPONDING GAMMA-PYRONES CARRYING ADJACENT CHIRAL CENTERS TOWARD BIOMIMETIC SYNTHESIS OF FULLY SUBSTITUTED GAMMA-PYRONE-CONTAINING NATURAL-PRODUCTS [J].

ARIMOTO, H ;

NISHIYAMA, S ;

YAMAMURA, S .

TETRAHEDRON LETTERS, 1990, 31 (39) :5619-5620

[3] Highly active chiral ruthenium catalysts for asymmetric cross- and ring-opening cross metathesis [J].

Berlin, Jacob M. ;

Goldberg, Steven D. ;

Grubbs, Robert H. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2006, 45 (45) :7591-7595

[4]

BERLIN JM, 2006, ANGEW CHEM, V118, P7753

[5] All-carbon quaternary stereogenic centers by enantioselective Cu-catalyzed conjugate additions promoted by a chiral N-heterocyclic carbene [J].

Brown, M. Kevin ;

May, Tricia L. ;

Baxter, Carl A. ;

Hoveyda, Amir H. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2007, 46 (07) :1097-1100

[6]

BURKE SD, 1999, ORG LETT, V1, P9720

[7] A general model for selectivity in olefin cross metathesis [J].

Chatterjee, AK ;

Choi, TL ;

Sanders, DP ;

Grubbs, RH .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (37) :11360-11370

[8]

Connon S. J, 2003, Angew. Chem, V115, P1944

[9] Recent developments in olefin cross-metathesis [J].

Connon, SJ ;

Blechert, S .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2003, 42 (17) :1900-1923

[10] Enantioselective copper-catalyzed conjugate addition to trisubstituted cyclohexenones: Construction of stereogenic quaternary centers [J].

d'Augustin, M ;

Palais, L ;

Alexakis, A .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2005, 44 (09) :1376-1378

← 1 2 3 4 5 →