Nickel-Catalysis Enabling α-Alkylation of Ketones by Secondary Alcohols

被引:15
作者
Bains, Amreen K. [1 ]
Biswas, Ayanangshu [1 ]
Kundu, Abhishek [1 ]
Adhikari, Debashis [1 ]
机构
[1] Indian Inst Sci Educ & Res IISER Mohali, Dept Chem Sci, Sas Nagar 140306, Punjab, India
关键词
Borrowing hydrogen; Secondary alcohol; Radical reaction; Azo-ligand redox; BORROWING HYDROGEN; DEHYDROGENATION; AUTOTRANSFER;
D O I
10.1002/adsc.202200522
中图分类号
O69 [应用化学];
学科分类号
081704 ;
摘要
The alpha-alkylation of ketones utilizing a secondary alcohol has been accomplished by an isolable, bench-stable, inexpensive nickel catalyst affording high yields of beta,beta-disubstituted products. This report contributes a nickel catalyst in the pool of a few scarce examples of base metal discovered for this purpose. The substrate scope can span a wide range including aliphatic, alicyclic, and cyclic secondary alcohols. Functionalization of a cholesterol molecule is also possible following this methodology. The catalyst can interconvert between azo and hydrazo form in a reversible fashion to enable this chemical transformation.
引用
收藏
页码:2815 / 2821
页数:7
相关论文
共 51 条
[1]   Stereoselective Synthesis of Cyclohexanes via an Iridium Catalyzed (5+1) Annulation Strategy [J].
Akhtar, Wasim M. ;
Armstrong, Roly J. ;
Frost, James R. ;
Stevenson, Neil G. ;
Donohoe, Timothy J. .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2018, 140 (38) :11916-11920
[2]   Hydrogen Borrowing Catalysis with Secondary Alcohols: A New Route for the Generation of β-Branched Carbonyl Compounds [J].
Akhtar, Wasim M. ;
Cheong, Choon Boon ;
Frost, James R. ;
Christensen, Kirsten E. ;
Stevenson, Neil G. ;
Donohoe, Timothy J. .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2017, 139 (07) :2577-2580
[3]   First-Row Transition Metal (De)Hydrogenation Catalysis Based On Functional Pincer Ligands [J].
Alig, Lukas ;
Fritz, Maximilian ;
Schneider, Sven .
CHEMICAL REVIEWS, 2019, 119 (04) :2681-2751
[4]   Nickel: The "Spirited Horse" of Transition Metal Catalysis [J].
Ananikov, Valentine P. .
ACS CATALYSIS, 2015, 5 (03) :1964-1971
[5]  
[Anonymous], 2015, ANGEW CHEM, V127, P14691
[6]  
[Anonymous], 2016, ANGEW CHEM, V128, P872
[7]  
[Anonymous], 2016, ANGEW CHEM, V128, P15191
[8]   Stereoselective synthesis of alicyclic ketones: A hydrogen borrowing approach [J].
Armstrong, Roly J. ;
Akhtar, Wasim M. ;
Frost, James R. ;
Christensen, Kirsten E. ;
Stevenson, Neil G. ;
Donohoe, Timothy J. .
TETRAHEDRON, 2019, 75 (48)
[9]   Solvent-Free N-Alkylation and Dehydrogenative Coupling Catalyzed by a Highly Active Pincer-Nickel Complex [J].
Arora, Vinay ;
Dutta, Moumita ;
Das, Kanu ;
Das, Babulal ;
Srivastava, Hemant Kumar ;
Kumar, Akshai .
ORGANOMETALLICS, 2020, 39 (11) :2162-2176
[10]   Nickel-Catalyzed Selective Synthesis of α-Alkylated Ketones via Dehydrogenative Cross-Coupling of Primary and Secondary Alcohols [J].
Bains, Amreen K. ;
Biswas, Ayanangshu ;
Adhikari, Debashis .
ADVANCED SYNTHESIS & CATALYSIS, 2022, 364 (01) :47-52