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DOI: 10.1055/s-0033-1341225
π-Excess σ2 P,O Hybrid Ligands: Synthesis of the First 4-Methoxy-1H-1,3-benzazaphospholes
Publication History
Received: 14 February 2014
Accepted after revision: 20 March 2014
Publication Date:
24 April 2014 (online)
Abstract
The synthesis of the first 4-methoxy-substituted 1,3-benzazaphosphole was accomplished by using a C,O-dilithium intermediate generated from N-(3-methoxyphenyl)-2,2-dimethylpropanamide and butyllithium. This intermediate was subjected either to direct phosphonylation or to a bromination and phosphonylation sequence; subsequent reductive cyclization with excess lithium aluminum hydride led to the desired product. In addition, N-(2,2-dimethylpropyl)-3-methoxy-2-phosphinoaniline, formed in a side reaction, was cyclized with (dimethoxymethyl)dimethylamine to give 1-(2,2-dimethylpropyl)-4-methoxy-1H-1,3-benzazaphosphole. The behavior of these +M-substituted π-excess aromatic σ2 P-heterocycles towards moisture is reported, together with their 1H, 13C, and 31P solution NMR spectra and a crystal-structure analysis. The new compounds represent potential σ2 P,O hybrid or chelate ligands with a high π-density at the phosphorus atom.
Supporting Information
- for this article is available online at http://www.thieme-connect.com/ejournals/toc/synthesis.
- Supporting Information
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