Ligand-Controlled Ruthenium-Catalyzed Borrowing-Hydrogen and Interrupted-Borrowing-Hydrogen Methodologies: Functionalization of Ketones Using Methanol as a C1 Source

被引:9
作者
Biswal, Priyabrata [1 ]
Subramani, M. Siva [1 ]
Samser, Shaikh [1 ]
Chandrasekhar, Vadapalli [2 ,3 ]
Venkatasubbaiah, Krishnan [1 ]
机构
[1] OCC Homi Bhabha Natl Inst, Natl Inst Sci Educ & Res, Sch Chem Sci, Bhubaneswar 752050, Odisha, India
[2] Tata Inst Fundamental Res Hyderabad, Hyderabad 500046, India
[3] Indian Inst Technol Kanpur, Dept Chem, Kanpur 208016, Uttar Pradesh, India
关键词
ONE-POT SYNTHESIS; GENOTOXIC IMPURITIES; METHYLATION; 1,5-DIKETONES; ALKYLATION; ALCOHOLS;
D O I
10.1021/acs.joc.2c00653
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
Herein we report simple, highly efficient, and phosphine-free N,C-Ru and N,N-Ru catalysts for ligand-controlled borrowing-hydrogen (BH) and interrupted-borrowing-hydrogen (I-BH) methods, respectively. This protocol has been employed on a variety of ketones using MeOH as a green, sustainable, and alternative C1 source to form a C-C bond through the BH and I-BH methods. Reasonably good substrate scope, functional group tolerance, and good-to-excellent yields at 70 degrees C are the added highlights of these methodologies. Controlled experiments reveal that an in situ formed formaldehyde is one of the crucial elements in this ligand-controlled selective protocol, which upon reaction with a ketone generates an enone as an intermediate. This enone in the presence of the N,C-Ru catalyst and N,N-Ru catalyst through the BH and I-BH pathways yields methylated ketones and 1,5-diketones, respectively.
引用
收藏
页码:5135 / 5146
页数:12
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