Chem. Rev. 1990, 90. 997-1025
9s7
Chemistry of 3-Membered Carbon-Phosphorus Heterocycles FRANFOIS MATHEY
Laboraloke de Chimi# du phosphore ef des Mhux de Transnkm Dcpn. E
d PM&n/que,
9 1126 Palalseau Ce&x, France
ReceivedJanuary IO, 1990 (Revised Manuscrip1ReceivedJune 6, 1990)
Contents 1. Introduction
11. Synthesis A. Phosphiranes I. From P and C, Units 2. From PC and C Units 3. By Cyclization of a P-C-C Unit 4. By Cyclization of a C-P-C Unit 5. Synthesis of Polycyclic Phosphiranes E. Phosphirenes 1. From P and C2 Units 2. From PC and C Units: Synthesis of 2H-Phosphirenes 3. By Cyclization of a C-P-C Unk C. Diphosphiranes 1. From P, and C Units 2. From PC and P Units 3. By Cyclization of a P-C-P Unit 4. Synthesis of Polycyclic Diphosphiranes D. Diphosphirenes 111. Physicochemical Data and Theoretical Problems A. Phosphiranes 1. Structural Data 2. Spectroscopic Data 3. Theoretical Calculations E. Phosphirenes 1. Structural, Spectroscopic, and Theoretical Data 2. Aromaticity Problem C. Diphosphiranes I V . Chemical Properties A. Phosphiranes 1. Reactions wim Retention of the Ring 2. Reactions with Cleavage of the Two P-C Bonds of the Ring 3. Reactions with Cleavage of One P-C Bond of the Ring 4. Ring Expansions E. Phosphirenes 1. Reactions wim Retention of the Ring 2. Reactions with Cleavage of the Two P-C Bonds of the Ring 3. Reactions with Cleavage of One P-C Bond of the Ring 4. Reactions at the C==C Double Bond 5. Ring Expansions C. Diphosphiranes V. Conclusion
997 998 998 996 999 1000 1000 1001 1002 1002 1003 1004 1004 1004 1005 1006 1006 1006 1007 1007 1007 1007 1007 1009 1009 1010 1012 1013 1013 1013 1014 1015 1015 1017 1018 1019 1019 1020 1020 1022 1022
I . Infroductlon The parent oxirane (ethylene oxide) was discovered as early as 1859 by Wurtz. Today, millions of tons of 0009-2665/90/0790-0997$09.50/0
Francois Mathey is Rofessor of Chemistry at Ecob Polytechnique. Palaiseau (near Paris). France, and "Directeur de Recherche" in Centre National de la Recherche Scientmque (CNRS). He was bom in Paris in 1941. studied in Ec& Polytechnique from 1961 to 1963. and then received a Ph.D. in organic chemishy from the University of Paris V I in 1971. He was appointed group leader in lnstiut National de Recherche Chimique Appiiquee (IRCHA) in 1969. lefl IRCHA for SociBt6 Nationale des Poudres et Explosifs (SNPE) in 1980, and, finalv. joined the facum at Ecob Po4ytechnique in 1987 and CNRS in 1989. His research deals with wganophosphorus and transition-metai chemistry. oxirane are produced each year by t h e chemical industry. The compound i s mainly used in the preparat i o n of ethylene glycols and poly(ethy1ene glycols) a n d for the manufacture of polymers. T h e story of aziridines also started very early. In 1888, Gabriel prepared the parent compound, which he formulated as vinylamine. The correct formulation was soon established by Marckwald. Today, some aziridines are produced commercially and are used in textiles, plastics, coatings, and drugs (e.g., anticancer drugs). These brief considerations underline the paramount importance of 3membered heterocycles in organic chemistry. As already stated in a previous review on phosphole chemistry,' the heterocyclic chemistry of phosphorus i s deeply underdeveloped by comparison w i t h i t s oxygen, nitrogen, and sulfur counterparts. In t h e case of three-membered heterocycles, the story started in 1963 w i t h the discovery of phosphiranes by Wagner? To say t h e least, t h i s discovery was considered w i t h some skepticism3 until it was confirmed in 1967.' Then, Baudler succeeded in preparing the first stable diphosphirane in 1978.5 The next breakthrough came in 1982 when M a r i n e t t i a n d Mathey unambiguously characterized the phosphirene ring! T h e story was completed w i t h t h e discovery of the first stable 2Hphosphirene by Regitz in 1987 and by t h e characterization o f the diphosphirene ring by Niecke in 1989 (see sections II.B.2 a n d 1I.D). Several reviews have been already w r i t t e n on three-membered phosphorus rings:-'* but they are now obsolete because progress in the field i s extremely fast. In this review, we have
0 1990 American Chemical Socbly
998 Chemical Reviews, 1990, Vol. 90,No. 6
attempted to comprehensively cover the literature until the middle of 1989.
[RP=M(CO)5]
+
Mathey
-
‘C=C
C=C
c=c
