Alternative Synthesis and Structures of C-monoacetylenic Phosphaalkenes

作者：Orthaber Andreas; Oberg Elisabet; Jane Reuben T; Ott Sascha^*

来源：Zeitschrift fur Anorganische und Allgemeine Chemie, 2012, 638(14): 2219-2224.

DOI：10.1002/zaac.201200324

• Phosphaalkenes
• Sonogashira coupling
• Hay coupling
• X-ray crystallography

An alternative synthesis of C-monoacetylenic phosphaalkenes trans-Mes*P=C(Me)(C=CR) (Mes* = 2,4,6-(Bu3Ph)-Bu-t, R = Ph, SiMe3) from C-bromophosphaalkenes cis-Mes*P=C(Me)Br using standard Sonogashira coupling conditions is described. Crystallographic studies confirm cis-trans isomerization of the P=C double bond during Pd-catalyzed cross coupling, leading exclusively to trans-acetylenic phosphaalkenes. Crystallographic studies of all synthesized compounds reveal the extend of pi-conjugation over the acetylene and P=C pi-systems.

• 出版日期2012-11