Enantioselective Palladium-Catalyzed Oxidative Cascade Cyclization of Aliphatic Alkenyl Amides

被引：46

作者：

Du, Wei ^{[1
,3
]}

Gu, Qiangshuai ^{[1
]}

Li, Yang ^{[2
,4
]}

Lin, Zhenyang ^{[2
]}

Yang, Dan ^{[1
]}

机构：

[1] Univ Hong Kong, Dept Chem, Pokfulam Rd, Hong Kong, Hong Kong, Peoples R China

[2] Hong Kong Univ Sci & Technol, Dept Chem, Kowloon, Hong Kong, Peoples R China

[3] Sichuan Univ, West China Sch Pharm, Chengdu 610041, Peoples R China

[4] Dalian Univ Technol, Sch Petr & Chem Engn, Panjin 124221, Peoples R China

来源：

ORGANIC LETTERS | 2017年 / 19卷 / 02期

关键词：

CARBOAMINATION REACTIONS; UNACTIVATED ALKENES; CYCLIC SULFAMIDES; SPRIX LIGAND; DIAMINATION; OLEFINS; BOND; AMINOPALLADATION; REARRANGEMENTS; RECOGNITION;

D O I：

10.1021/acs.orglett.6b03410

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The catalyst system of Pd(TFA)(2)/(S,S)-diPh-pyrox is reported to promote the highly efficient enantioselective oxidative cascade cyclization of alkene-tethered aliphatic acrylamides under mild aerobic conditions. A series of pyrrolizidine derivatives have been synthesized in good yield and excellent enantioselectivity. Deuterium-labeling experiments have revealed that the reaction proceeded through an anti-aminopalladation (anti-AP) pathway with high selectivity. The transition states for the anti-AP step have been calculated to account for the observed enantioselectivity.

引用

页码：316 / 319

页数：4

共 56 条

[1] PALLADIUM-PROMOTED ADDITION OF AMINES TO ISOLATED DOUBLE-BONDS [J].

AKERMARK, B ;

BACKVALL, JE ;

HEGEDUS, LS ;

ZETTERBE.K ;

SIIRALAH.K ;

SJOBERG, K .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1974, 72 (01) :127-138

[2] Transition-Metal-Catalyzed Allylic Substitutions of Trichloroacetimidates [J].

Arnold, Jeffrey S. ;

Zhang, Qi ;

Nguyen, Hien M. .

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2014, 2014 (23) :4925-4948

[3] Desymmetrization of meso-2,5-Diallylpyrrolidinyl Ureas through Asymmetric Palladium-Catalyzed Carboamination: Stereocontrolled Synthesis of Bicyclic Ureas [J].

Babij, Nicholas R. ;

Wolfe, John P. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2013, 52 (35) :9247-9250

[4] EVIDENCE FOR REVERSIBLE AMINOPALLADATION OF OLEFINS [J].

BACKVALL, JE ;

BJORKMAN, EE .

ACTA CHEMICA SCANDINAVICA SERIES B-ORGANIC CHEMISTRY AND BIOCHEMISTRY, 1984, 38 (01) :91-93

[5] Development of Chiral Spiro Ligands for Metal-Catalyzed Asymmetric Reactions [J].

Bajracharya, Gan B. ;

Arai, Midori A. ;

Koranne, Priti S. ;

Suzuki, Takeyuki ;

Takizawa, Shinobu ;

Sasai, Hiroaki .

BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, 2009, 82 (03) :285-302

[6] Dual Palladium(II)/Tertiary Amine Catalysis for Asymmetric Regioselective Rearrangements of Allylic Carbamates [J].

Bauer, Johannes Moritz ;

Frey, Wolfgang ;

Peters, Rene .

CHEMISTRY-A EUROPEAN JOURNAL, 2016, 22 (16) :5767-5777

[7] Asymmetric Cascade Reaction to Allylic Sulfonamides from Allylic Alcohols by Palladium(II)/Base-Catalyzed Rearrangement of Allylic Carbamates [J].

Bauer, Johannes Moritz ;

Frey, Wolfgang ;

Peters, Rene .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2014, 53 (29) :7634-7638

[8] Palladium(II)-Catalyzed Enantioselective Reactions Using COP Catalysts [J].

Cannon, Jeffrey S. ;

Overman, Larry E. .

ACCOUNTS OF CHEMICAL RESEARCH, 2016, 49 (10) :2220-2231

[9] Mechanistic studies of a palladium-catalyzed intramolecular hydroamination of unactivated alkenes: Protonolysis of a stable palladium alkyl complex is the turnover-limiting step [J].

Cochran, Brian M. ;

Michael, Forrest E. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2008, 130 (09) :2786-2792

[10] Catalytic Asymmetric Synthesis of Cyclic Sulfamides from Conjugated Dienes [J].

Cornwall, Richard G. ;

Zhao, Baoguo ;

Shi, Yian .

ORGANIC LETTERS, 2013, 15 (04) :796-799

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