Iterative Dual-Metal and Energy Transfer Catalysis Enables Stereodivergence in Alkyne Difunctionalization: Carboboration as Case Study.

Autor:	Corpas J; Department of Organic Chemistry, Faculty of Science; Institute for Advanced Research in Chemical Sciences (IAdChem); and Centro de Innovación en Química Avanzada (ORFEO-CINQA), Universidad Autónoma de Madrid (UAM), Cantoblanco, 28049 Madrid, Spain., Gomez-Mendoza M; Photoactivated Processes Unit, IMDEA Energy Institute, Technological Park of Mostoles, Avda. Ramón de la Sagra 3, 28935 Madrid, Spain., Arpa EM; Division of Theoretical Chemistry, IFM, Linköping University, 581 83 Linköping, Sweden., de la Peña O'Shea VA; Photoactivated Processes Unit, IMDEA Energy Institute, Technological Park of Mostoles, Avda. Ramón de la Sagra 3, 28935 Madrid, Spain., Durbeej B; Division of Theoretical Chemistry, IFM, Linköping University, 581 83 Linköping, Sweden., Carretero JC; Department of Organic Chemistry, Faculty of Science; Institute for Advanced Research in Chemical Sciences (IAdChem); and Centro de Innovación en Química Avanzada (ORFEO-CINQA), Universidad Autónoma de Madrid (UAM), Cantoblanco, 28049 Madrid, Spain., Mauleón P; Department of Organic Chemistry, Faculty of Science; Institute for Advanced Research in Chemical Sciences (IAdChem); and Centro de Innovación en Química Avanzada (ORFEO-CINQA), Universidad Autónoma de Madrid (UAM), Cantoblanco, 28049 Madrid, Spain., Arrayás RG; Department of Organic Chemistry, Faculty of Science; Institute for Advanced Research in Chemical Sciences (IAdChem); and Centro de Innovación en Química Avanzada (ORFEO-CINQA), Universidad Autónoma de Madrid (UAM), Cantoblanco, 28049 Madrid, Spain.
Jazyk:	angličtina
Zdroj:	ACS catalysis [ACS Catal] 2023 Nov 03; Vol. 13 (22), pp. 14914-14927. Date of Electronic Publication: 2023 Nov 03 (Print Publication: 2023).
DOI:	10.1021/acscatal.3c03570
Abstrakt:	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 β-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. Competing Interests: The authors declare no competing financial interest. (© 2023 The Authors. Published by American Chemical Society.)
Databáze:	MEDLINE
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