Asymmetric Synthesis of Remote Quaternary Centers by Copper-Catalyzed Desymmetrization: An Enantioselective Total Synthesis of (+)-Mesembrine

被引：28

作者：

Bokka, Apparao ^{[1
]}

Mao, James X. ^{[1
]}

Hartung, John ^{[2
]}

Martinez, Steven R. ^{[2
]}

Simanis, Justin A. ^{[2
]}

Nam, Kwangho ^{[1
]}

Jeon, Junha ^{[1
]}

Shen, Xiaoqiang ^{[2
]}

机构：

[1] Univ Texas Arlington, Dept Chem & Biochem, Arlington, TX 76019 USA

[2] AbbVie Inc, Proc Res & Dev, 1 North Waukegan Rd, N Chicago, IL 60064 USA

来源：

ORGANIC LETTERS | 2018年 / 20卷 / 17期

关键词：

SUBSTITUTED CYCLIC ENONES; ARYL ALUMINUM REAGENTS; ALPHA-ARYLATION; CONJUGATE ADDITION; STEREOGENIC CENTERS; ALLYLIC ALKYLATION; TRISUBSTITUTED ENONES; ARYLBORONIC ACIDS; CARBOXYLIC-ACIDS; CUH;

D O I：

10.1021/acs.orglett.8b02084

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Catalytic asymmetric syntheses of remote quaternary stereocenters have been developed by copper-catalyzed 1,4-hydrosilylation of gamma,gamma-disubstituted cyclohexadienones. A variety of cyclohexenones have been synthesized in good yield and excellent enantioselectivity. Versatile 2-silyloxy diene intermediates bearing gamma,gamma-disubstituted all carbon stereogenic centers can be isolated from the mild reaction conditions. The utility of this strategy is exemplified in a catalytic asymmetric total synthesis of (+)-mesembrine.

引用

页码：5158 / 5162

页数：5

共 59 条

[41] Asymmetric Induction at Remote Quaternary Centers of Cyclohexadienones by Rhodium-Catalyzed Conjugate Hydrosilylation [J].

Naganawa, Yuki ;

Kawagishi, Mayu ;

Ito, Jun-ichi ;

Nishiyama, Hisao .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2016, 55 (24) :6873-6876

[42]

Nicolaou KC, 2002, ANGEW CHEM INT EDIT, V41, P1668, DOI 10.1002/1521-3773(20020517)41:10<1668::AID-ANIE1668>3.0.CO

[43]

2-Z

[44] Enantioselective Synthesis of α-Quaternary Mannich Adducts by Palladium-Catalyzed Allylic Alkylation: Total Synthesis of (+)-Sibirinine [J].

Numajiri, Yoshitaka ;

Pritchett, Beau P. ;

Chiyoda, Koji ;

Stoltz, Brian M. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2015, 137 (03) :1040-1043

[45] Copper Hydride Catalyzed Hydroamination of Alkenes and Alkynes [J].

Pirnot, Michael T. ;

Wang, Yi-Ming ;

Buchwald, Stephen L. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2016, 55 (01) :48-57

[46] Catalytic enantioselective synthesis of quaternary carbon stereocentres [J].

Quasdorf, Kyle W. ;

Overman, Larry E. .

NATURE, 2014, 516 (7530) :181-191

[47] Sodium Tetraarylborates as Effective Nucleophiles in Rhodium/Diene-Catalyzed 1,4-Addition to β,β-Disubstituted α,β-Unsaturated Ketones: Catalytic Asymmetric Construction of Quaternary Carbon Stereocenters [J].

Shintani, Ryo ;

Tsutsumi, Yosuke ;

Nagaosa, Makoto ;

Nishimura, Takahiro ;

Hayashi, Tamio .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2009, 131 (38) :13588-+

[48] Palladium-Catalyzed Asymmetric Conjugate Addition of Arylboronic Acids to α,β-Unsaturated Cyclic Electrophiles [J].

Shockley, Samantha E. ;

Holder, Jeffrey C. ;

Stoltz, Brian M. .

ORGANIC PROCESS RESEARCH & DEVELOPMENT, 2015, 19 (08) :974-981

[49] Total Synthesis of (+)-Mesembrine Applying Asymmetric Gold Catalysis [J].

Spittler, Michael ;

Lutsenko, Kiril ;

Czekelius, Constantin .

JOURNAL OF ORGANIC CHEMISTRY, 2016, 81 (14) :6100-6105

[50] Regio- and enantioselective Pd-catalyzed allylic alkylation of ketones through allyl enol carbonates [J].

Trost, BM ;

Xu, JY .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (09) :2846-2847

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