Abstract
The mechanisms of the gold(I)-catalyzed rearrangement of homopropargyl sulfoxides have been investigated using density functional theory calculations done at the B3LYP/6-31G(d, p) (SDD for Au) level of theory. Solvent effects on these reactions have been explored by calculations that included a polarizable continuum model (PCM) for the solvent (CH2Cl2). Two plausible pathways which lead to the formation of benzothiepinones or benzothiopines via an α-carbonyl Au carbenoid through 5-exo-dig cyclization or 6-endo-dig cyclization were proposed. Our calculation results suggested the following. (1) The first step of the cycle is nucleophilic addition of the sulfoxide oxygen onto the triple bond to form an alkenyl gold intermediate through 5-exo-dig cyclization or 6-endo-dig cyclization. The alkenyl gold species is then capable of pushing out the sulfide moiety, forming an α-carbonyl Au carbenoid. Finally, α-carbonyl Au carbenoids undergo intramolecular Friedel–Crafts alkylation to produce the observed products ...
Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
