Nickel-Catalyzed Hydroborylative Polycyclization of Allenynes: an Atom-Economical and Diastereoselective Synthesis of Bicyclic 5-5 Fused Rings
EntityUAM. Departamento de Química Orgánica
10.1002/adsc.202101462Advanced Synthesis & Catalysis 364.10 (2022): 1716-1723
ISSN1615-4150 (print); 1615-4169 (online)
Funded byWe thank the support by MICIU (CTQ2016-79826-R and PID2019- 109088GB-I00) and for a FPI fellowship to I. M. M. We also thank the Centro de Computación Científica-UAM for technical assistance. We thank Juan Carlos Nieto-Carmona for helpful discussion and Prof. Fernando P. Cossío for helpful calculations
ProjectGobierno de España. CTQ2016-79826-R
SubjectsAllenes; Cyclization.; Hydroboration; Ni; Reaction mechanisms; Química
Rights© 2022 The Authors
Esta obra está bajo una licencia de Creative Commons Reconocimiento-NoComercial-SinObraDerivada 4.0 Internacional.
A diastereoselective synthesis of borylated bicyclic 5-5 fused ring systems by a domino Ni-catalyzed hydroborylative polycyclization of allenynes has been developed. The reaction provides two new C−C and one C−B bonds and constitutes an atom-economical method. It occurs rapidly, in absence of inert atmosphere, with an inexpensive Ni-based catalyst and HBpin as boron source. The procedure showed excellent tolerance to functional groups and a wide scope. Derivatization of the borylated bicycles has been performed to explore the synthetic utility of the products. Experimental and DFT-calculation results suggest that the process starts by an oxidative cyclometallation involving Ni(0) and both the allene and the alkyne moieties, followed by a stereoselective σ-metathesis with HBpin. Formation of the second ring takes place through a non-fully coplanar 1,2-insertion into the Ni−H bond to give a nickelacyclohexene which finally evolves by reductive elimination. (Figure presented)
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Google Scholar:Manjón Mata, Inés - Quirós, M. Teresa - Velasco Juárez, Elena - Buñuel Magdalena, María Elena - Cárdenas, Diego J.
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