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Synthesis 2011(9): 1477-1483  
DOI: 10.1055/s-0030-1259964
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Propylphosphonic Anhydride (T3P®)-Mediated One-Pot Rearrangement of Carboxylic Acids to Carbamates

John Kallikat Augustine*a, Agnes Bombrunb, Ashis Baran Mandala, Padma Alagarsamya, Rajendra Nath Attaa, Panneer Selvama
a Syngene International Ltd., Biocon Park, Plot Nos. 2 & 3, Bommasandra IV Phase, Jigani Link Road, Bangalore - 560 099, India
Fax: +91(80)28083150; e-Mail: john.kallikat@syngeneintl.com;
b Merck Serono SA, 9 Chemin des Mines, 1202 Geneva, Switzerland
Further Information

Publication History

Received 5 February 2011
Publication Date:
22 March 2011 (online)

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Abstract

A simple one-pot conversion of carboxylic acids to carbamates is achieved by propylphosphonic anhydride (T3P®) in combination with azidotrimethylsilane and an alcohol via the Curtius­ rearrangement. Besides diverse primary to tertiary alcohols, the reaction tolerated a wide scope of aromatic, heterocyclic, and ­aliphatic carboxylic acids which underwent rearrangement in ­excellent yields.

Key words

propylphosphonic anhydride - Curtius rearrangement - carbamates - peptide coupling agents - azidotrimethylsilane

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9

For a review on TMSN3, see ref. 2c.

10

The enantiomeric excess was determined by SFC (supercritical-fluid chromatography) using a Chiracel OD column. There was no erosion of the enantiomeric excess during the process and a difference of 1% ee is within the experimental error.