Enantioselective Folding of Enynes by Gold(I) Catalysts with a Remote C2-Chiral Element

被引：66

作者：

Zuccarello, Giuseppe ^{[1
,2
]}

Mayans, Joan G. ^{[1
,2
]}

Escofet, Imma ^{[1
,2
]}

Scharnagel, Dagmar ^{[1
]}

Kirillova, Manila S. ^{[1
]}

Perez-Jimeno, Alba H. ^{[1
,2
]}

Calleja, Pilar ^{[1
]}

Boothe, Jordan R. ^{[1
]}

Echavarren, Antonio M. ^{[1
,2
]}

机构：

[1] Barcelona Inst Sci & Technol, Inst Chem Res Catalonia ICIQ, Av Paisos Catalans 16, Tarragona 43007, Spain

[2] Univ Rovira & Virgili, Dept Quim Organ & Analit, C Marcel Li Domingo S-N, Tarragona 43007, Spain

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2019年 / 141卷 / 30期

关键词：

ABSOLUTE-CONFIGURATION; LIGANDS; CAREXANES; ARYLALKYNES; DERIVATIVES; 1,3-ENYNES; ASSIGNMENT; RESOLUTION; COMPLEXES; MOLECULES;

D O I：

10.1021/jacs.9b06326

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Chiral gold(I) catalysts have been designed based on a modified JohnPhos ligand with a distal C-2-2,5-diarylpyrrolidine that creates a tight binding cavity. The C-2-chiral element is close to where the C-C bond formation takes place in cyclizations of 1,6-enynes. These chiral mononuclear catalysts have been applied for the enantioselective 5-exo-dig and 6-endo-dig cyclization of different 1,6-enynes as well as in the first enantioselective total synthesis of three members of the carexane family of natural products. Opposite enantioselectivities have been achieved in seemingly analogous reactions of 1,6-enynes, which result from different chiral folding of the substrates based on attractive aryl aryl interactions.

引用

页码：11858 / 11863

页数：6

共 43 条

[1] The synthesis of substituted phosphathiahelicenes via regioselective bromination of a preformed helical scaffold: a new approach to modular ligands for enantioselective gold-catalysis [J].

Aillard, Paul ;

Dova, Davide ;

Magne, Valentin ;

Retailleau, Pascal ;

Cauteruccio, Silvia ;

Licandro, Emanuela ;

Voituriez, Arnaud ;

Marinetti, Angela .

CHEMICAL COMMUNICATIONS, 2016, 52 (73) :10984-10987

[2] Well-Defined Chiral Gold(III) Complex Catalyzed Direct Enantioconvergent Kinetic Resolution of 1,5-Enynes [J].

Bohan, Patrick T. ;

Toste, F. Dean .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2017, 139 (32) :11016-11019

[3] Product Divergence in Coinage-Metal-Catalyzed Reactions of π-Rich Compounds [J].

Boyle, Joshua William ;

Zhao, Yichao ;

Chan, Philip Wai Hong .

SYNTHESIS-STUTTGART, 2018, 50 (07) :1402-1416

[4] THERMAL REACTIONS OF ALKYL N-CARBOMETHOXYSULFAMATE ESTERS [J].

BURGESS, EM ;

PENTON, HR ;

TAYLOR, EA .

JOURNAL OF ORGANIC CHEMISTRY, 1973, 38 (01) :26-31

[5] Structural biology and chemistry of the terpenoid cyclases [J].

Christianson, David W. .

CHEMICAL REVIEWS, 2006, 106 (08) :3412-3442

[6] Carexanes:: prenyl stilbenoid derivatives from Carex distachya [J].

D'Abrosca, B ;

Fiorentino, A ;

Golino, A ;

Monaco, P ;

Oriano, P ;

Pacifico, S .

TETRAHEDRON LETTERS, 2005, 46 (32) :5269-5272

[7] Gold-Catalyzed Cycloisomerizations of 1,n-Diyne Carbonates and Esters [J].

Day, David Philip ;

Chan, Philip Wai Hong .

ADVANCED SYNTHESIS & CATALYSIS, 2016, 358 (09) :1368-1384

[8] Development of Chiral Bis-hydrazone Ligands for the Enantioselective Cross-Coupling Reactions of Aryldimethylsilanolates [J].

Denmark, Scott E. ;

Chang, Wen-Tau T. ;

Houk, K. N. ;

Liu, Peng .

JOURNAL OF ORGANIC CHEMISTRY, 2015, 80 (01) :313-366

[9] REGIOSELECTIVITY IN THE ALKALINE THIOLATE DEPROTECTION OF ARYL METHYL ETHERS [J].

DODGE, JA ;

STOCKSDALE, MG ;

FAHEY, KJ ;

JONES, CD .

JOURNAL OF ORGANIC CHEMISTRY, 1995, 60 (03) :739-741

[10] Gold(I)-Catalyzed Activation of Alkynes for the Construction of Molecular Complexity [J].

Dorel, Ruth ;

Echavarren, Antonio M. .

CHEMICAL REVIEWS, 2015, 115 (17) :9028-9072

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