Cyclopropenylidenephosphoranes: Rearrangement to Azetidinylidene-Methylphosphoniums

Autor:	Remi Chauvin, Carine Duhayon, Jordi Poater, Cleve Dionel Mboyi, Albert Poater
Přispěvatelé:	Laboratoire de chimie de coordination (LCC), Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie de Toulouse (ICT-FR 2599), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut de Química Computacional i Catàlisi and Departament de Química, Universitat de Girona (IQCC), Universitat de Girona (UdG), Institució Catalana de Recerca i Estudis Avançats (ICREA), Universitat de Barcelona (UB), Spanish MCIU : projects PGC2018-097722-BI00, CTQ2016-77558-R, MDM-2017-0767
Rok vydání:	2020
Předmět:	chemistry.chemical_compound Tetrafluoroborate 010405 organic chemistry Chemistry Organic Chemistry Polymer chemistry [CHIM.COOR]Chemical Sciences/Coordination chemistry 010402 general chemistry 01 natural sciences 0104 chemical sciences
Zdroj:	Journal of Organic Chemistry Journal of Organic Chemistry, American Chemical Society, 2020, 85 (11), pp.7452-7458. ⟨10.1021/acs.joc.0c00847⟩
ISSN:	1520-6904 0022-3263
DOI:	10.1021/acs.joc.0c00847⟩
Popis:	International audience; Attempts at preparing cyclopropenylphosphonium salts by P-quaternization of α-aminophosphines with bisdiisopropylaminocyclopropenium tetrafluoroborate led to azetidin-2-ylidene methylphosphoniums as unexpected isomers, in 57-85 % yield. The basic structure of the products is discussed on the basis of X-ray crystallography analysis. The unprecedented 3→4 ring expansion process is argued to be driven by an ambivalent aromatic vs anti-aromatic character (or loss of aromaticity) of the primary phosphonium product. On the basis of DFT calculations, a mechanism involving a concerted 1,4-hydride shift/electrocyclization process as the rate determining step is proposed and discussed vs possible alternatives.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_dedup___::b27fb98d17532ef61bc10179a78ea936 https://pubmed.ncbi.nlm.nih.gov/32391694 Zobrazit plný text záznamu