期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 141, 期 7, 页码 3006-3013出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.8b11395
关键词
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资金
- UC Irvine
- National Institutes of Health [R35GM127071]
- National Science Foundation [CHE-1465263]
- Liaocheng University
- NSF Graduate Research Fellowship
In this Article, we expand upon the catalytic hydrothiolation of 1,3-dienes to afford either allylic or homoallylic sulfides with high regiocontrol. Mechanistic studies support a pathway in which regioselectivity is dictated by the choice of counterion associated with the Rh center. Non-coordinating counterions, such as SbF6-, allow for eta(4)-diene coordination to Rh complexes and result in allylic sulfides. In contrast, coordinating counterions, such as Cl-, favor neutral Rh complexes in which the diene binds 172 to afford homoallylic sulfides. We propose mechanisms that rationalize a fractional dependence on thiol for the 1,2-Markovnikov hydrothiolation while accounting for an inverse dependence on thiol in the 3,4-anti-Markovnikov pathway. Through the hydrothiolation of an essential oil (beta-farnesene), we achieve the first enantioselective synthesis of (-)-agelasidine A.
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