78424-79-0Relevant articles and documents
Catalytic Hydrothiolation: Counterion-Controlled Regioselectivity
Yang, Xiao-Hui,Davison, Ryan T.,Nie, Shao-Zhen,Cruz, Faben A.,McGinnis, Tristan M.,Dong, Vy M.
supporting information, p. 3006 - 3013 (2019/02/19)
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 η4-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 η2 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 (β-farnesene), we achieve the first enantioselective synthesis of (-)-agelasidine A.
2-HYDROXYMETHYL-4-PHENYLTHIO-1-BUTENE AS A KEY COMPOUND FOR TOTAL SYNTHESIS OF ACYCLIC TERPENOIDS
Mandai, Tadakatsu,Yamaguchi, Hirofumi,Nishikawa, Kengo,Kawada, Mikio,Otera, Junzo
, p. 763 - 764 (2007/10/02)
A new total synthesis of myrcene, citral, squalane, and isophytol employing 2-hydroxymethyl-4-phenylthio-1-butene as a starting material is described.
