211675-18-2Relevant academic research and scientific papers
Allyl 4-Chlorophenyl Sulfone as a Versatile 1,1-Synthon for Sequential α-Alkylation/Cobalt-Catalyzed Allylic Substitution
Kojima, Masahiro,Matsunaga, Shigeki
, p. 1934 - 1946 (2020/07/03)
Despite their unique potential as rare 1,1-dipole synthons, allyl sulfones are rarely used in target-oriented syntheses, likely due to the lack of a general catalytic method for their branch-selective allylic substitution. Herein, we identified allyl 4-chlorophenyl sulfone as a versatile linchpin for both base-mediated α-derivatization and subsequent cobalt-catalyzed allylic substitution. The sequential transformations allow for highly regioselective access to branched allylic substitution products with a variety of aliphatic side chains. The photoredox-enabled cobalt catalysis is indispensable for achieving high yields and regioselectivity for the desulfonylative substitution in contrast to traditional metal-catalyzed protocols, which lead to inferior outcomes in the corresponding transformations.
Palladium-catalyzed carbene insertion and trapping with carbon nucleophiles
Devine, Sean K. J.,Van Vranken, David L.
supporting information; experimental part, p. 1909 - 1911 (2009/04/18)
Palladium catalysts are shown to catalyze the three-component coupling of vinyl halides, trimethylsilyldiazomethane. and stabilized carbon nucleophiles. The reaction is believed to proceed through a palladium-carbene intermediate LX(R)Pd=CHSiMe3 that undergoes migration of the vinyl substituent to the electrophilic carbene center to generate an ν3-allylpalladium intermediate. The allylpalladium intermediate is attacked by the carbon nucleophile to generate a vinylsilane product.
