Development of Chemo- and Enantioselective Palladium-Catalyzed Decarboxylative Asymmetric Allylic Alkylation of α-Nitroesters

被引：21

作者：

Trost, Barry M. ^{[1
]}

Schultz, Johnathan E. ^{[1
]}

Bai, Yu ^{[1
]}

机构：

[1] Stanford Univ, Dept Chem, Stanford, CA 94305 USA

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2019年 / 58卷 / 34期

关键词：

allylic alkylation; asymmetric catalysis; chemoselectivity; enantioselectivity; palladium catalysis; QUATERNARY CARBON STEREOCENTERS; ONE-POT SYNTHESIS; STEREOABLATIVE REACTIONS; C-ALKYLATION; NITROALKANES; ALLYLATION; ESTERS; ACID; CONSTRUCTION; DIASTEREO;

D O I：

10.1002/anie.201904034

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

We describe the development of a Pd-catalyzed decarboxylative asymmetric allylic alkylation of alpha-nitro allyl esters to afford acyclic tetrasubstituted nitroalkanes. Optimization of the reaction parameters revealed unique ligand and solvent combinations crucial for achieving chemo- and enantioselective C-alkylation of electronically challenging benzylic nitronates and sterically encumbered 2-allyl esters. Substrates were efficiently accessed in a combinatorial fashion by a cross-Claisen/ alpha-arylation sequence. The method provides functional group orthogonality that complements nucleophilic imine allylation strategies for alpha-tertiary amine synthesis.

引用

收藏

页码：11820 / 11825

页数：6

相关论文

共 56 条

[1] Enantioselective Synthesis of α-Allyl-α-aryldihydrocoumarins and 3-lsochromanones via Pd-Catalyzed Decarboxylative Asymmetric Allylic Alkylation [J].

Akula, Ramulu ;

Guiry, Patrick J. .

ORGANIC LETTERS, 2016, 18 (21) :5472-5475

[2] Palladium-catalyzed enantioselective decarboxylative allylic alkylation of fully substituted N-acyl indole-derived enol carbonates [J].

Alexy, Eric J. ;

Fulton, Tyler J. ;

Zhang, Haiming ;

Stoltz, Brian M. .

CHEMICAL SCIENCE, 2019, 10 (23) :5996-6000

[3] Catalytic Enantioselective Synthesis of Acyclic Quaternary Centers: Palladium-Catalyzed Decarboxylative Allylic Alkylation of Fully Substituted Acyclic Enol Carbonates [J].

Alexy, Eric J. ;

Zhang, Haiming ;

Stoltz, Brian M. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2018, 140 (32) :10109-10112

[4]

[Anonymous], 2001, The Nitro Group in Organic Synthesis

[5] Advances in Stereoconvergent Catalysis from 2005 to 2015: Transition-Metal-Mediated Stereoablative Reactions, Dynamic Kinetic Resolutions, and Dynamic Kinetic Asymmetric Transformations [J].

Bhat, Vikram ;

Welin, Eric R. ;

Guo, Xuelei ;

Stoltz, Brian M. .

CHEMICAL REVIEWS, 2017, 117 (05) :4528-4561

[6] Structure-Based Rationale for Selectivity in the Asymmetric Allylic Alkylation of Cycloalkenyl Esters Employing the Trost 'Standard Ligand' (TSL): Isolation, Analysis and Alkylation of the Monomeric form of the Cationic η3-Cyclohexenyl Complex [(η3-c-C6H9)Pd(TSL)]+ [J].

Butts, Craig P. ;

Filali, Emane ;

Lloyd-Jones, Guy C. ;

Norrby, Per-Ola ;

Sale, David A. ;

Schramm, York .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2009, 131 (29) :9945-9957

[7] ALPHA-NITRO KETONES AND ESTERS FROM ACYLIMIDAZOLES [J].

CRUMBIE, RL ;

NIMITZ, JS ;

MOSHER, HS .

JOURNAL OF ORGANIC CHEMISTRY, 1982, 47 (21) :4040-4045

[8] Iridium-catalyzed enantioselective allylic substitutions with aliphatic nitro compounds as prenucleophiles [J].

Dahnz, A ;

Helmchen, G .

SYNLETT, 2006, (05) :697-700

[9] Nickel-Catalyzed Asymmetric C-Alkylation of Nitroalkanes: Synthesis of Enantioenriched β-Nitroamides [J].

Devannah, Vijayarajan ;

Sharma, Rajgopal ;

Watson, Donald A. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2019, 141 (21) :8436-8440

[10] Metal-Free C-Arylation of Nitro Compounds with Diaryliodonium Salts [J].

Dey, Chandan ;

Lindstedt, Erik ;

Olofsson, Berit .

ORGANIC LETTERS, 2015, 17 (18) :4554-4557

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