Enantioselective Copper(I)-Catalyzed Alkynylation of Oxocarbenium Ions to Set Diaryl Tetrasubstituted Stereocenters

被引：60

作者：

Dasgupta, Srimoyee ^{[1
]}

Rivas, Thomas ^{[1
]}

Watson, Mary P. ^{[1
]}

机构：

[1] Univ Delaware, Dept Chem & Biochem, Newark, DE 19716 USA

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2015年 / 54卷 / 47期

基金：

美国国家科学基金会;

关键词：

alkynes; asymmetric catalysis; enantioselectivity; oxocarbenium ion; oxygen heterocycles; CATALYTIC ASYMMETRIC-SYNTHESIS; COPPER(I) COMPLEXES; KETONES; ETHERS; TRANSFORMATION; REDUCTION; ACETYLIDE; DINUCLEAR; ALDEHYDES; ADDITIONS;

D O I：

10.1002/anie.201507373

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

An enantioselective, copper(I)-catalyzed addition of terminal alkynes to isochroman ketals to set diaryl, tetrasubstituted stereocenters has been developed. The success of this reaction relies on identification of a Cu/PyBox catalyst capable of distinguishing the faces of the diaryl-substituted oxocarbenium ion. This challenging transformation enables efficient conversion of readily available, racemic ketals into high-value enantioenriched isochroman products with fully substituted stereogenic centers. High yields and enantiomeric excesses are observed for various isochroman ketals and an array of alkynes.

引用

页码：14154 / 14158

页数：5

共 60 条

[51] Lithium ephedrate-mediated addition of a lithium acetylide to a ketone: Solution structures and relative reactivities of mixed aggregates underlying the high enantioselectivities [J].

Thompson, A ;

Corley, EG ;

Huntington, MF ;

Grabowski, EJJ ;

Remenar, JF ;

Collum, DB .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (09) :2028-2038

[52] USE OF AN EPHEDRINE ALKOXIDE TO MEDIATE ENANTIOSELECTIVE ADDITION OF AN ACETYLIDE TO A PROCHIRAL KETONE - ASYMMETRIC-SYNTHESIS OF THE REVERSE-TRANSCRIPTASE INHIBITOR L-743,726 [J].

THOMPSON, AS ;

CORLEY, EG ;

HUNTINGTON, MF ;

GRABOWSKI, EJJ .

TETRAHEDRON LETTERS, 1995, 36 (49) :8937-8940

[53] A catalytic enantioselective approach to chromans and chromanols. A total synthesis of (-)-calanolides A and B and the vitamin E nucleus [J].

Trost, BM ;

Toste, FD .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (35) :9074-9075

[54] Enzyme-catalyzed enantioselective diaryl ketone reductions [J].

Truppo, Matthew D. ;

Pollard, David ;

Devine, Paul .

ORGANIC LETTERS, 2007, 9 (02) :335-338

[55]

Unterhalt B, 2002, PHARMAZIE, V57, P346

[56] Catalytic enantioselective allylboration of ketones [J].

Wada, R ;

Oisaki, K ;

Kanai, M ;

Shibasaki, M .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (29) :8910-8911

[57] An efficient catalytic asymmetric epoxidation method [J].

Wang, ZX ;

Tu, Y ;

Frohn, M ;

Zhang, JR ;

Shi, Y .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1997, 119 (46) :11224-11235

[58]

Witten M.R., 2014, Angew. Chem, V126, P6022, DOI DOI 10.1002/ANGE.201402834

[59] Catalytic Asymmetric Synthesis of 8-Oxabicyclooctanes by Intermolecular [5+2] Pyrylium Cycloadditions [J].

Witten, Michael R. ;

Jacobsen, Eric N. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2014, 53 (23) :5912-5916

[60] A general catalytic allylation using allyltrimethoxysilane [J].

Yamasaki, S ;

Fujii, K ;

Wada, R ;

Kanai, M ;

Shibasaki, M .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (23) :6536-6537

← 1 2 3 4 5 6 →