Catalytic Hydrothiolation: Counterion-Controlled Regioselectivity.
Yang XH , Davison RT , Nie SZ , Cruz FA , McGinnis TM , Dong VM 
J Am Chem Soc.2019 Feb 08 ; ():.
PubMedで表示
Google翻訳で開く
(2view , 0users)
Full Text Sources
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 SbF, allow for η-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 η 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.
PMID: 30735362 [PubMed - as supplied by publisher]
PMID: 30735362 [PubMed - as supplied by publisher]
関連論文
- Synthesis of 1,1-disubstituted alkyl vinyl sulfides via rhodium-catalyzed alkyne hydrothiolation: scope and limitations.
- [Review] Organo-f-element catalysts for efficient and highly selective hydroalkoxylation and hydrothiolation.
- Ligand-Controlled Regioselectivity in the Hydrothiolation of Alkynes by Rhodium N-Heterocyclic Carbene Catalysts.
- Rhodium-Catalyzed Regiodivergent Hydrothiolation of Allyl Amines and Imines.
- Catalytic Hydrothiolation: Regio- and Enantioselective Coupling of Thiols and Dienes.