77411-99-5Relevant academic research and scientific papers
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.
A VERSATILE METHOD FOR ALLYLIC SULFIDE SYNTHESIS
Sato, Tsuneo,Hiramura, Yasuaki,Otera, Junzo,Nozaki, Hitosi
, p. 2821 - 2824 (2007/10/02)
A practical method for synthesizing a variety of allylic sulfides has been developed through Wittig(-Horner) reaction of α-sulfenylated aldehydes which are readily accessible from methoxy(phenylthio)methane.
The Formation of Allyl Sulphides by Phenylthio-migration: Control by Silicon
Fleming, Ian,Paterson, Ian,Pearce, Andrew
, p. 256 - 262 (2007/10/02)
When γ-silyl-β-phenylthio-alcohols are treated with acid, the strategically placed silyl group encourages the rearrangement of the phenylthio-group, both from a secondary migration origin to a secondary migration terminus, and from a secondary migration origin to a tertiary migration terminus (4)->(6).Geraniol/nerol (12) and linalool (14) have been synthesised from a common intermediate (11) using this type of reaction.Phenylthio-migration from a tertiary migration origin (17)->(3) can be controlled to a limited extent by a suitably placed silyl group, but it is easier to achieve direct β-elimination of the silyl and phenylthio-groups (17)->(18).
