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Synthesis 2012; 44(15): 2424-2430
DOI: 10.1055/s-0031-1290396
DOI: 10.1055/s-0031-1290396
paper
Thiol-Free Synthesis of Oseltamivir and Its Analogues via Organocatalytic Michael Additions of Oxyacetaldehydes to 2-Acylaminonitroalkenes
Further Information
Publication History
Received: 30 March 2012
Accepted after revision: 09 May 2012
Publication Date:
13 June 2012 (online)
Abstract
The organocatalytic addition of substituted oxyacetaldehydes to 2-acylaminonitroethenes proceeded with good to high diastereoselectivities and enantioselectivities. The resulting adducts reacted with ethyl 2-(diethoxyphosphoryl) acrylate to afford highly functionalized cyclohexenes. A thiol-free protocol for cyclization has been developed that leads to a separable mixture of two diastereoisomers. The unwanted diastereoisomer can be efficiently epimerized. The resulting cyclohexenes are precursors to oseltamivir and its analogues. The synthesis of the key reagent, 3-pentyloxyaldehyde, was also improved.
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