104508-12-5Relevant 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 Substitutions of Allylic Nitro Compounds. Regiochemistry
Tamura, Rui,Kai, Yoshiki,Kakihana, Masato,Hayashi, Koji,Tsuji, Masanori,et al.
, p. 4375 - 4385 (2007/10/02)
Primary, secondary, and tertiary allylic nitro compounds underwent Pd(0)-catalyzed allylic substitution by stabilized carboanions, secondary amines, and benzenesulfinate ion (PhSO2-). α,β-disubstituted α-nitro olefins also behaved as allylic nitro compounds, via base-catalyzed vinyl -> allyl rearrangement, and underwent allylic substitution by secondary amines and PhSO2-.The regiochemistry of these substitutions was dependent on the structure of the allylic nitro compound amd on the steric bulk of the nucleophile.Generally, substitution occurred at the lesshindered or least substituted site.In some cases added or generated NaNO2 affected the regioselectivity of the allylic substitution of allylic nitro compounds and some allylic acetates by PhSO2-.Under these conditions, the more sterically hindered allylic sulfones were formed.
