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Highly efficient synthesis of 3,4-diarylbutadiene sulfones using Heck-Matsuda reaction.

ABSTRACT: For the first time we describe a general method for the synthesis of previously not synthesized unsymmetrical 3,4-diarylbutadiene sulfones which can be stable convenient precursors for 2,3-diaryl-1,3-butadienes. Our method for arylation of butadiene sulfones via Heck-Matsuda reaction allows to obtain unsymmetrical 3,4-diarylbutadiene sulfones with a variety of alkyl, alkoxy, nitro, ethoxycarbonyl, perfluoroalkyl and halogen substituents (30 examples) in very good yields using readily available reagents and catalysts.

SUBMITTER: Shurupova OV

PROVIDER: S-EPMC8981374 | biostudies-literature | 2022 Feb

REPOSITORIES: biostudies-literature

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Highly efficient synthesis of 3,4-diarylbutadiene sulfones using Heck-Matsuda reaction.

Shurupova Olga V OV Rzhevskiy Sergey A SA Minaeva Lidiya I LI Topchiy Maxim A MA Asachenko Andrey F AF

RSC advances 20220215 9

For the first time we describe a general method for the synthesis of previously not synthesized unsymmetrical 3,4-diarylbutadiene sulfones which can be stable convenient precursors for 2,3-diaryl-1,3-butadienes. Our method for arylation of butadiene sulfones <i>via</i> Heck-Matsuda reaction allows to obtain unsymmetrical 3,4-diarylbutadiene sulfones with a variety of alkyl, alkoxy, nitro, ethoxycarbonyl, perfluoroalkyl and halogen substituents (30 examples) in very good yields using readily avai ...[more]

PMID: 35425582

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Project description:The use of more than one catalyst in one-pot reaction conditions has become a rapidly evolving protocol in the development of asymmetric catalysis. The lack of molecular insights on the mechanism and enantioselectivity in dual-catalytic reactions motivated the present study focusing on an important catalytic asymmetric Heck-Matsuda cross-coupling. A comprehensive density functional theory (M06 and B3LYP-D3) investigation of the coupling between a spirocyclic cyclopentene and 4-fluorophenyl diazonium species under a dual-catalytic condition involving Pd2(dba)3 (dba = trans, trans-dibenzylideneacetone) and chiral 2,2'-binaphthyl diamine (BINAM)-derived phosphoric acids (BDPA, 2,2'-binaphthyl diamine-derived phosphoric acids) is presented. Among various mechanistic possibilities examined, the pathway with explicit inclusion of the base (in situ generated sodium bicarbonate/sodium biphosphate) is found to be energetically more preferred over the analogous base-free routes. The chiral phosphate generated by the action of sodium carbonate on BDPA is found to remain associated with the reaction site as a counterion. The initial oxidative addition of Pd(0) to the aryl diazonium bond gives rise to a Pd-aryl intermediate, which then goes through the enantiocontrolling migratory insertion to the cyclic alkene, leading to an arylated cycloalkene intermediate. Insights on how a series of noncovalent interactions, such as C-H···O, C-H···N, C-H···F, C-H···π, lp···π, O-H···π, and C-F···π, in the enantiocontrolling transition state (TS) render the migration of the Pd-aryl to the si prochiral face of the cyclic alkene more preferred over that to the re face are utilized for modulating the enantioselectivity. Aided by molecular insights on the enantiocontrolling transition states, we predicted improved enantioselectivity from 37% to 89% by changes in the N-aryl substituents of the catalyst. Subsequent experiments in our laboratory offered very good agreement with the predicted enantioselectivities.

Dataset Information

Highly efficient synthesis of 3,4-diarylbutadiene sulfones using Heck-Matsuda reaction.

Publications

Highly efficient synthesis of 3,4-diarylbutadiene sulfones using Heck-Matsuda reaction.

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