The reaction of pyrroles and indoles with B(C6F5)3 and BCl3 produces 1:1 B-N complexes containing highly acidic sp3 carbons, for example, N-[tris(pentafluorophenyl)borane]-5H-pyrrole (1) and N-[tris(pentafluorophenyl)borane]-3H-indole (2), that are formed by a new formal N-to-C hydrogen shift, the mechanism of which is discussed. With some derivatives, restricted rotation around the B-N bond and/or the B-C bonds was observed by NMR techniques, and some rotational barriers were calculated from experimental data. The acidity of the sp3 carbons in these complexes is shown by their ability to protonate NEt3, with formation of pyrrolyl- and indolyl-borate ammonium salts. The driving force for this reaction is given by the restoration of the aromaticity of the heterocycle.

Synthesis and reactivity of (C6F5)3B-N-heterocycle complexes. 1. Generation of highly acidic sp3 carbons in pyrroles and indoles / S. Guidotti, I. Camurati, F. Focante, L. Angellini, G. Moscardi, L. Resconi, R. Leardini, D. Nanni, P. Mercandelli, A. Sironi, T. Beringhelli, D. Maggioni. - In: JOURNAL OF ORGANIC CHEMISTRY. - ISSN 0022-3263. - 68:14(2003), pp. 5445-5465.

Synthesis and reactivity of (C6F5)3B-N-heterocycle complexes. 1. Generation of highly acidic sp3 carbons in pyrroles and indoles

P. Mercandelli;A. Sironi;T. Beringhelli
Penultimo
;
D. Maggioni
Ultimo
2003

Abstract

The reaction of pyrroles and indoles with B(C6F5)3 and BCl3 produces 1:1 B-N complexes containing highly acidic sp3 carbons, for example, N-[tris(pentafluorophenyl)borane]-5H-pyrrole (1) and N-[tris(pentafluorophenyl)borane]-3H-indole (2), that are formed by a new formal N-to-C hydrogen shift, the mechanism of which is discussed. With some derivatives, restricted rotation around the B-N bond and/or the B-C bonds was observed by NMR techniques, and some rotational barriers were calculated from experimental data. The acidity of the sp3 carbons in these complexes is shown by their ability to protonate NEt3, with formation of pyrrolyl- and indolyl-borate ammonium salts. The driving force for this reaction is given by the restoration of the aromaticity of the heterocycle.
Settore CHIM/03 - Chimica Generale e Inorganica
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/2434/184804
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