期刊
ACS CATALYSIS
卷 13, 期 22, 页码 14914-14927出版社
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.3c03570
关键词
cooperative catalysis; energy transfer catalysis; stereodivergence; tetrasubstituted olefins; alkenyl boronates; beta-boryl acrylates; photoisomerization
This article demonstrates the synthesis of stereodivergent tetrasubstituted beta-boryl acrylates through iterative dual-metal and energy transfer catalysis. The reluctance of electron-deficient internal alkynes to undergo catalytic carboboration has been overcome through cooperative Cu/Pd-catalysis, while an Ir complex acts as a versatile sensitizer for photoisomerization of the resulting sterically crowded alkenes.
Stereochemically defined tetrasubstituted olefins are widespread structural elements of organic molecules and key intermediates in organic synthesis. However, flexible methods enabling stereodivergent access to E and Z isomers of fully substituted alkenes from a common precursor represent a significant challenge and are actively sought after in catalysis, especially those amenable to complex multifunctional molecules. Herein, we demonstrate that iterative dual-metal and energy transfer catalysis constitutes a unique platform for achieving stereodivergence in the difunctionalization of internal alkynes. The utility of this approach is showcased by the stereodivergent synthesis of both stereoisomers of tetrasubstituted beta-boryl acrylates from internal alkynoates with excellent stereocontrol via sequential carboboration and photoisomerization. The reluctance of electron-deficient internal alkynes to undergo catalytic carboboration has been overcome through cooperative Cu/Pd-catalysis, whereas an Ir complex was identified as a versatile sensitizer that is able to photoisomerize the resulting sterically crowded alkenes. Mechanistic studies by means of quantum-chemical calculations, quenching experiments, and transient absorption spectroscopy have been applied to unveil the mechanism of both steps.
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