Fragmentation-related phosphinylations using 2-aryl-2-phosphabicyclo[2.2.2]oct- 5-ene- and -octa-5,7-diene 2-oxides

• Published in: Heteroatom chemistry Vol. 14; no. 5; pp. 443 - 451
• Main Authors: Keglevich, György, Szelke, Helga, Bálint, Ágnes, Imre, Tímea, Ludányi, Krisztina, Nagy, Zoltán, Hanusz, Miklós, Simon, Kálmán, Harmat, Veronika, Tőke, László
• Format: Journal Article
• Language: English
• Published: Hoboken Wiley Subscription Services, Inc., A Wiley Company 2003
• ISSN: 1042-7163; 1098-1071
• DOI: 10.1002/hc.10176

A series of new P‐methylphenyl P‐heterocycles are introduced. The para and ortho substituted 2,5‐dihydro‐1H‐phosphole oxides (1a and 1b) were converted to the double‐bond isomers (A and B) of 1,2‐dihydrophosphinine oxides (3a and 3b) via the corresponding phosphabicyclo[3.1.0]hexane oxides (2a or 2b). Isomeric mixture (A and B) of the dihydrophosphinine oxides (3a and 3b) gave, in turn, the isomers (A and B) of phosphabicyclo[2.2.2]oct‐5‐enes (4a and 4b) or a phosphabicyclo[2.2.2]octa‐5,7‐diene (5) in Diels‐Alder reaction with dienophiles. The bridged P‐heterocycles (4 and 5) were useful in the photo‐ or thermoinduced fragmentation‐related phosphinylation of hydroxy compounds and amines. The new precursors (4a and 4b) were applied in mechanistic investigations. © 2003 Wiley Periodicals, Inc. Heteroatom Chem 14:443–451, 2003; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.10176