Catalytic Aerobic Carbooxygenation for the Construction of Vicinal Tetrasubstituted Centers: Application to the Synthesis of Hexasubstituted γ-Lactones.

Autor: Pünner F; Synthetic Organic Chemistry Laboratory, RIKEN Cluster for Pioneering Research, 2-1 Hirosawa, Wako, 351-0198, Saitama, Japan.; Catalysis and Integrated Research Group, RIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako, 351-0198, Saitama, Japan., Sohtome Y; Synthetic Organic Chemistry Laboratory, RIKEN Cluster for Pioneering Research, 2-1 Hirosawa, Wako, 351-0198, Saitama, Japan.; Catalysis and Integrated Research Group, RIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako, 351-0198, Saitama, Japan.; Organic & Biomolecular Chemistry Laboratory Department of Applied Chemistry College of Life Sciences, Ritsumeikan University, Kusatsu, 525-8577, Shiga, Japan., Lyu Y; Catalysis and Integrated Research Group, RIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako, 351-0198, Saitama, Japan., Hashizume D; Materials Characterization Support Team, RIKEN Center for Emergent Matter Science, 2-1 Hirosawa, Wako, 351-0198, Saitama, Japan., Akakabe M; Synthetic Organic Chemistry Laboratory, RIKEN Cluster for Pioneering Research, 2-1 Hirosawa, Wako, 351-0198, Saitama, Japan.; Catalysis and Integrated Research Group, RIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako, 351-0198, Saitama, Japan., Yoshimura M; Molecular Ligand Target Research Team, RIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako, 351-0198, Saitama, Japan., Yashiroda Y; Molecular Ligand Target Research Team, RIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako, 351-0198, Saitama, Japan., Yoshida M; Chemical Genomics Research Group, RIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako, 351-0198, Saitama, Japan., Sodeoka M; Synthetic Organic Chemistry Laboratory, RIKEN Cluster for Pioneering Research, 2-1 Hirosawa, Wako, 351-0198, Saitama, Japan.; Catalysis and Integrated Research Group, RIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako, 351-0198, Saitama, Japan.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2024 Sep 02; Vol. 63 (36), pp. e202405876. Date of Electronic Publication: 2024 Aug 02.
DOI: 10.1002/anie.202405876
Abstrakt: Strategic design for the construction of contiguous tetrasubstituted carbon centers represents a daunting challenge in synthetic organic chemistry. Herein, we report a combined experimental and computational investigation aimed at developing catalytic aerobic carbooxygenation, involving the intramolecular addition of tertiary radicals to geminally disubstituted alkenes, followed by aerobic oxygenation. This reaction provides a straightforward route to various α,α,β,β-tetrasubstituted γ-lactones, which can be readily transformed into hexasubstituted γ-lactones through allylation/translactonization. Computational analysis reveals that the key mechanistic foundation for achieving the developed aerobic carbooxygenation involves the design of endothermic (energetically uphill) C-C bond formation followed by exothermic (energetically downhill) oxygenation. Furthermore, we highlight a unique fluorine-induced stereoelectronic effect that stabilizes the endothermic stereodetermining transition state.
(© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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