Issue 18, 2011

C,C-Diacetylenic phosphaalkenes in palladium-catalyzed cross-coupling reactions

Abstract

The reactivity of bis-TMS-substituted C,C-diacetylenic phosphaalkene (A2PA) 1 in Sonogashira–Hagihara cross-coupling reactions has been examined. The selective and successive deprotection of the two silyl groups in 1 is enabled by the steric bulk of the Mes* group which renders the acetylenetrans to Mes* more reactive and thereby facilitates selective and consecutive couplings with iodoarenes. In situ transformation of the TMS-protected acetylenes into Cu(I)acetylides is the key step in the synthetic sequence and enables the preparation of the first dimeric A2PA linked by a phenylene spacer. cis–transIsomerization across the P[double bond, length as m-dash]C bond is triggered by a tertiary amine and exclusively observed in the case of nitrophenyl-substituted A2PAs. The introduced aryl groups are integral parts of the entire π-system as evidenced by spectroscopic and electrochemical studies.

Graphical abstract: C,C-Diacetylenic phosphaalkenes in palladium-catalyzed cross-coupling reactions

Supplementary files

Article information

Article type
Paper
Submitted
04 May 2011
Accepted
02 Jun 2011
First published
27 Jul 2011

Org. Biomol. Chem., 2011,9, 6246-6255

C,C-Diacetylenic phosphaalkenes in palladium-catalyzed cross-coupling reactions

E. Öberg, X. Geng, M. Santoni and S. Ott, Org. Biomol. Chem., 2011, 9, 6246 DOI: 10.1039/C1OB05705G

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements