Phenylcopper-Boron Trifluoride Etherate1

PhCu + BF3.OEt2

[3220-49-3]  · C6H5Cu  · Phenylcopper-Boron Trifluoride Etherate  · (MW 140.66) (BF3.OEt2)

[109-63-7]  · C4H10BF3O  · Phenylcopper-Boron Trifluoride Etherate  · (MW 141.95)

(selective nucleophilic reagent for substitution reactions2,3 and conjugate additions1)

Physical Data: see entries for individual components.

Preparative Method: prepared by the addition of Boron Trifluoride Etherate to a suspension of Phenylcopper in diethyl ether or tetrahydrofuran at -70 °C.2

Handling, Storage, and Precautions: see entries for individual components. Use in a fume hood.

Nucleophilic Substitutions.

Substitution reactions involving phenylcopper/BF3 exhibit chemoselectivities, rates, and regioselectivities which are similar to those observed with alkylcopper/BF3 (see Methylcopper-Boron Trifluoride Etherate). In the presence of Tri-n-butylphosphine, phenylcopper/BF3 adds to chiral enal acetals in an SN2 substitution (eq 1). The result, on hydrolysis of the enol ether, is an effective asymmetric conjugate addition to the enal.4

Conjugate Additions.

Again, the observed chemistry is similar to that observed with alkylcopper/BF3.

1. Yamamoto, Y. AG(E) 1986, 25, 947.
2. Yamamoto, Y.; Yamomoto, S.; Yatagai, H.; Maruyama, K. JACS 1980, 102, 2318.
3. Normant, J. F.; Alexakis, A.; Ghribi, A.; Mangeney, P. T 1989, 45, 507.
4. Mangeney, P.; Alexakis, A.; Normant, J. F. TL 1987, 28, 2363.

John N. Haseltine

Georgia Institute of Technology, Atlanta, GA, USA

Copyright 1995-2000 by John Wiley & Sons, Ltd. All rights reserved.