89510-58-7Relevant academic research and scientific papers
Palladium-Catalyzed Regio- A nd Enantioselective Hydrosulfonylation of 1,3-Dienes with Sulfinic Acids: Scope, Mechanism, and Origin of Selectivity
Dong, Dongfang,Zhang, Qinglong,Zi, Weiwei
supporting information, p. 15860 - 15869 (2020/10/18)
Chiral sulfones are important structural motifs in organic synthesis because of their widespread use in pharmaceutical chemistry. In particular, chiral allylic sulfones have drawn particular interest because of their synthetic utility. However, enantioselective synthesis of 1,3-disubstituted unsymmetrical chiral allylic sulfones remains a challenge. In this article, we report a protocol for (R)-DTBM-Segphos/Pd-catalyzed regio- A nd enantioselective hydrosulfonylation of 1,3-dienes with sulfinic acids, which provides atom- A nd step-economical access to 1,3-disubstituted chiral allylic sulfones. The reaction occurs under mild conditions and has a broad substrate scope. Combined experimental and computational studies suggest that the reaction is initiated by a ligand-to-ligand hydrogen transfer followed by a C-S bond reductive elimination via a six-membered transition state. Steric repulsion between the olefinic C-H of the substrate and the tert-butyl group of (R)-DTBM-Segphos was found to be a key factor in the enantiocontrol.
Palladium-Catalyzed Syntheses of Aryl Polyenes
Mitsudo, Taki-aki,Fischetti, William,Heck, Richard F.
, p. 1640 - 1646 (2007/10/02)
The palladium-catalyzed arylation reaction has been employed to prepare a variety of mono- and diaryl 1,3-dienes and 1,3,5-trienes.The yields were good when electron withdrawing substituents were present in the aryl groups but only poor to fair when electron-donating groups were involved.Monoaryl dienes and trienes reacted well with all types of aryl halides to give mixed diaryl derivatives. 2-Bromostyrene reacts with phenylhexatriene to form 1,8-diphenyloctatetraene and with hexatriene to form 1,10-diphenyldecapentaene, but both only in about 15percent yield.
