Please use this identifier to cite or link to this item:
Type: Artigo de periódico
Title: Synthesis of B- and P-heterocycles by reaction of cyclic acetals and ketals with borinium and phosphonium ions
Author: Wang, F
Tao, WA
Gozzo, FC
Eberlin, MN
Cooks, RG
Abstract: Tricoordinated cyclic boron cations result from gas-phase ion/molecule reactions of dicoordinated borinium ions with neutral acetals and ketals and thiazolidine. The reaction, which proceeds via initial cationic binding to a heteroatom followed by a consecutive ring-opening and ring-reclosing process, resembles the Eberlin transacetalization of acylium ions (Eberlin, M. N.; Cooks, R. G. Org. Mass Spectrom. 1993, 28, 679). The cyclic structure of the tricoordinated boron cation is demonstrated by tandem mass spectrometry and further confirmed by comparison with authentic cyclic tricoordinated boron cations.; The five-membered cyclic boron cations dissociate by ethylene oxide loss to thus reform the reactant-dicoordinated borinium ion; the six-membered boron cations fragment instead by ethylene loss. Consistent with the proposed mechanism, the ion/molecule reaction efficiency falls in the order CH3OB+C2H5 > CH3OB+OCH3 much greater than CH3B+CH3; i.e., the higher the nucleophilicity of the borinium ion, the higher the reaction efficiency. A potential energy surface is calculated for the reaction of CH3OB+OCH3 with 2-methyl-1,3-dioxolane, and the reaction is found to be 43.3 kcal/mol exothermic due to initial formation of a strong B-O bond. The analogous reactivity displayed by phosphonium ions is also investigated by both experiment and ab initio calculations. In contrast to the borinium ions, the phosphonium ions exhibit higher regioselectivity for sulfur compared to nitrogen and oxygen. Finally, the present findings indicate that the reaction exothermicity and the regioselectivity are controlled by both the Lewis acidity of the reactant cations and the leaving ability of the released neutrals in the rate-limiting nucleophilic-induced recyclization step.
Country: EUA
Editor: Amer Chemical Soc
Citation: Journal Of Organic Chemistry. Amer Chemical Soc, v. 64, n. 9, n. 3213, n. 3223, 1999.
Rights: fechado
Identifier DOI: 10.1021/jo982446s
Date Issue: 1999
Appears in Collections:Unicamp - Artigos e Outros Documentos

Files in This Item:
File Description SizeFormat 
WOS000080171200043.pdf258.89 kBAdobe PDFView/Open

Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.