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Synthesis 2010(4): 579-586  
DOI: 10.1055/s-0029-1218589
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Synthesis of Benzoxazoles by an Efficient Ullmann-Type Intramolecular C(aryl)-O Bond-Forming Coupling Cyclization with a BINAM-Copper(II) Catalyst

Ajay B. Naidu, Govindasamy Sekar*
Department of Chemistry, Indian Institute of Technology Madras, Chennai, Tamil Nadu 600036, India
Fax: +91(44)22574202; e-Mail: gsekar@iitm.ac.in;
Further Information

Publication History

Received 2 October 2009
Publication Date:
07 December 2009 (online)

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Abstract

A wide range of 2-substituted benzoxazoles were synthesized from the corresponding N-(2-iodophenyl)benzamides through intramolecular C(aryl)-O bond formation via Ullmann-type coupling cyclization in the presence of a catalytic amount of an easily available BINAM-copper(II) complex under very mild reaction conditions (82 ˚C). Less reactive bromo and chloro analogues of the N-(2-halophenyl)benzamides were also successfully cyclized to produce benzoxazoles, without increasing the catalyst loading.

Key words

copper catalyst - nitrogen ligands - C-O bond formation - Ullmann coupling - benzoxazole synthesis

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17

BINAM with Cu(OTf)2 gives a 1:2 complex. The X-ray crystal structure of (R)-BINAM-Cu(OTf)2 complex was solved; see ref. 15d.

18

BINAM is irritating to the skin, eyes, and respiratory tract, and is an equivocal tumorigenic agent by RTECS criteria (as per the Material Safety Data Sheet of Strem Chemicals, Inc.).