Thermal Rearrangement of 1,5,8-Triphosphaisolumibullvalenes (1,5,8-Triphosphatetracyclo[4.4.0.02,8.05,7]deca-3,9-dienes)

✍ Scribed by Hendrik Disteldorf; Jens Renner; Heinrich Heydt; Paul Binger; Manfred Regitz

• Publisher: John Wiley and Sons
• Year: 2003
• Tongue: English
• Weight: 202 KB
• Volume: 2003
• Category: Article
• ISSN: 1434-193X
• DOI: 10.1002/ejoc.200300173

✦ Synopsis

Abstract

1,5,8‐Triphosphaisolumibullvalenes (1,5,8‐triphosphatetracyclo[4.4.0.0^2,8^.0^5,7^]deca‐3,9‐dienes) 3, when suitably substituted, undergo thermal rearrangement to afford the 1,1b,2a‐triphosphahomoquadricyclanes (tetrahydro‐1__H__‐1,1b,2a‐triphosphadicyclopropa[cd,gh]‐pentalenes) 6. The structure of the rearranged compound 6d was elucidated by X‐ray crystallography. The newly synthesized compound 6a undergoes addition of oxygen or sulfur with an increase in the coordination at the phosphorus atom P‐1 to yield the products 10a/b; it also undergoes complexation with Co~2~(CO)~8~ at the newly formed P−C≡C− unit to afford product 11. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)