Stoichiometric and Catalytic Synthesis of Alkynylphosphines 英文参考文献.docVIP

Molecules 2012, 17, 14573-14587; doi:10.3390/molecules171214573 OPEN ACCESS molecules ISSN 1420-3049 /journal/molecules Review Stoichiometric and Catalytic Synthesis of Alkynylphosphines Elise Bernoud, Romain Veillard, Carole Alayrac * and Annie-Claude Gaumont * Laboratoire de Chimie Moléculaire et Thioorganique, UMR CNRS 6507, INC3M FR3038, ENSICAEN Université de Caen Basse-Normandie, 14050 Caen, France; E-Mails: e.bernoud@ (E.B.); romain.veillard@ensicaen.fr (R.V.) * Authors to whom correspondence should be addressed; E-Mails: carole.witulski-alayrac@ensicaen.fr (C.A.); annie-claude.gaumont@ensicaen.fr (A.-C.G.); Tel.: +33-2-31-45-28-86 (C.A.); +33-2-31-45-28-73 (A.-C.G.); Fax: +33-2-31-45-28-77. Received: 23 November 2012; in revised form: 29 November 2012 / Accepted: 5 December 2012 / Published: 7 December 2012 Abstract: Alkynylphosphines or their borane complexes are available either through C–P bond forming reactions or through modification of the phosphorus or the alkynyl function of various alkynyl phosphorus derivatives. The latter strategy, and in particular the one involving phosphoryl reduction by alanes or silanes, is the method of choice for preparing primary and secondary alkynylphosphines, while the former strategy is usually employed for the synthesis of tertiary alkynylphosphines or their borane complexes. The classical C–P bond forming methods rely on the reaction between halophosphines or their borane complexes with terminal acetylenes in the presence of a stoichiometric amount of organometallic bases, which precludes the access to alkynylphosphines bearing sensitive functional groups. In less than a decade, efficient catalytic procedures, mostly involving copper complexes and either an electrophilic or a nucleophilic phosphorus reagent, have emerged. By proceeding under mild conditions, these new methods have allowed a significant broadening of the substituent