Regioselective and Stereospecific Rhodium-Catalyzed Allylic Cyanomethylation with an Acetonitrile Equivalent: Construction of Acyclic β-Quaternary Stereogenic Nitriles

被引：18
作者：
Tom, Mai Jan [1 ]
Evans, P. Andrew [1 ,2 ]
机构：
[1] Queens Univ, Dept Chem, Kingston, ON K7L 3N6, Canada
[2] Cent South Univ, Xiangya Sch Pharmaceut Sci, Changsha 410013, Hunan, Peoples R China
来源：
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2020年 / 142卷 / 28期
基金：
加拿大自然科学与工程研究理事会;
关键词：
CARBONYL-COMPOUNDS; SECONDARY ALCOHOLS; SUBSTITUTION; TRIMETHYLSILYLACETONITRILE; ALKYLATION; TERTIARY; REARRANGEMENT; CONVERSION;
D O I：
10.1021/jacs.0c02316
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
A highly regioselective and stereospecific rhodium-catalyzed cyanomethylation of tertiary allylic carbonates for the construction of acyclic beta-quaternary stereogenic nitriles is described. This protocol represents the first example of a metal-catalyzed allylic substitution reaction using a triorganosilyl-stabilized acetonitrile anion, which permits access to several carbonyl derivatives that are challenging to prepare using conventional pronucleophiles. The synthetic utility of the stereospecific cyanomethylation is further exemplified through the construction of an intermediate utilized in the total synthesis of both (-)-epilaurene and (-)-alpha-cuparenone.
引用
收藏
页码：11957 / 11961
页数：5
相关论文
共 53 条
[1]   Full Chirality Transfer in the Conversion of Secondary Alcohols into Tertiary Boronic Esters and Alcohols Using Lithiation-Borylation Reactions [J].
Bagutski, Viktor ;
French, Rosalind M. ;
Aggarwal, Varinder K. .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2010, 49 (30) :5142-5145
[2]   EQUILIBRIUM ACIDITIES IN DIMETHYL-SULFOXIDE SOLUTION [J].
BORDWELL, FG .
ACCOUNTS OF CHEMICAL RESEARCH, 1988, 21 (12) :456-463
[3]   Copper-Catalyzed Cyanomethylation of Allylic Alcohols with Concomitant 1,2-Aryl Migration: Efficient Synthesis of Functionalized Ketones Containing an α-Quaternary Center [J].
Bunescu, Ala ;
Wang, Qian ;
Zhu, Jieping .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2015, 54 (10) :3132-3135
[4]   Iridium-Catalyzed Enantioselective Allylic Substitution of Enol Silanes from Vinylogous Esters and Amides [J].
Chen, Ming ;
Hartwig, John F. .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2015, 137 (43) :13972-13979
[5]   Iridium-Catalyzed Regio- and Enantioselective Allylic Substitution of Silyl Dienolates Derived from Dioxinones [J].
Chen, Ming ;
Hartwig, John F. .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2014, 53 (45) :12172-12176
[6]   Iridium-Catalyzed Enantioselective Allylic Substitution of Unstabilized Enolates Derived from α,β-Unsaturated Ketone [J].
Chen, Ming ;
Hartwig, John F. .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2014, 53 (33) :8691-8695
[7]   Synthesis of 1-arylmethyl-2-(2-cyanoethyl)aziridines and their rearrangement into novel 2-(Aminomethyl)cyclopropanecarbonitriles [J].
D'hooghe, Matthias ;
Vervisch, Karel ;
De Kimpe, Norbert .
JOURNAL OF ORGANIC CHEMISTRY, 2007, 72 (19) :7329-7332
[8]   Enantioselective synthesis of all-carbon quaternary stereogenic centers in acyclic systems [J].
Das, Jaya Prakash ;
Marek, Ilan .
CHEMICAL COMMUNICATIONS, 2011, 47 (16) :4593-4623
[9]   Ureidopeptide- Based Bronsted Bases: Design, Synthesis and Application to the Catalytic Enantioselective Synthesis of b- Amino Nitriles from ( Arylsulfonyl) acetonitriles [J].
Diosdado, Saioa ;
Lopez, Rosa ;
Palomo, Claudio .
CHEMISTRY-A EUROPEAN JOURNAL, 2014, 20 (21) :6526-6531
[10]   Regio- and Enantiospecific Rhodium-Catalyzed Allylic Substitution with an Acyl Anion Equivalent [J].
Evans, P. Andrew ;
Oliver, Samuel .
ORGANIC LETTERS, 2013, 15 (22) :5626-5629
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