Directed, Remote Dirhodium C(sp3)-H Functionalization, Desaturative Annulation, and Desaturation

被引:9
作者
Munnuri, Sailu [1 ]
Falck, John R. [1 ]
机构
[1] Univ Texas Dallas, Dept Biochem & Pharmacol, Div Chem, Southwestern Med Ctr, Dallas, TX 75390 USA
关键词
H BOND FUNCTIONALIZATION; O-ALKYLATION; ESTERS;
D O I
10.1021/jacs.2c07427
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Iminodirhodium reactive intermediates generated in situ from O-tosyloximes using Rh2(esp)2 in CH2Cl2 at rt were exploited for an agile trichotomy of challenging transformations: (1) remote C-H functionalizations using an exceptionally broad diversity of inorganic and organic nucleophiles including several unconventional examples, for example, ethers and acyl silanes; (2) desaturative annulation, a biomimetic 1,3-methylene C-C ring-closure with an overall loss of two hydrogens; and (3) directed desaturation for the acceptor-less, regioselective creation of gamma,5- or gamma,5,e,C-olefins. Compared with typical iminyl transition-metal-mediated and 1,5-hydrogen atom-transfer (1,5-HAT) processes, iminodirhodium intermediates are largely underexplored, especially with respect to C(sp3)-H centers and, yet, have the potential to be transformative by virtue of their substrate breadth, regiocontrol, and elusive reaction modality. A substrate scope includes benzylic, allylic, propargylic, tertiary, and alpha-alkyloxy centers.
引用
收藏
页码:17989 / 17998
页数:10
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