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Synlett 2009(8): 1295-1298  
DOI: 10.1055/s-0028-1216726
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

A Practical and Highly Chemoselective Hydrogenation of Aldehydes with a Copper Catalyst

Hideo Shimizu*, Noboru Sayo, Takao Saito
Research & Development Division, Takasago International Corporation, 1-4-11, Nishi-yawata, Hiratsuka City, Kanagawa 254-0073, Japan
Fax: +81(463)252093; e-Mail: hideo_shimizu@takasago.com;
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Publication History

Received 27 January 2009
Publication Date:
17 April 2009 (online)

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Abstract

A practical hydrogenation of aldehydes mediated by an inexpensive and easily available base metal, copper, is reported. A copper complex associated with 1,4-bis(diphenylphosphino)butane (DPPB) hydrogenates α,β-unsaturated aldehydes in a highly chemoselective fashion to give allylic alcohols with improved catalytic productivities. The reaction system was also effective for the conversion of simple aldehydes to the corresponding alcohols.

Key words

hydrogenation - aldehydes - copper - homogeneous catalysis - chemoselectivity

    References and Notes

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7

Our attempt to hydrogenate (-)-4-(prop-1-en-2-yl)cyclo-hexen-1-carbaldehyde [(-)-perilaldehyde] at S/C = 500
with the condition described in ref. 6b, resulted in trace conversion. The reaction reportedly completed at S/C = 20, which was reproduced by us.

10

Representative Procedure (Table 1, Entry 1)
To a 100 mL stainless steel autoclave equipped with a glass inner lining and a Teflon-coated stirring bar were added [Cu(NO3)(PPh3)2] (11.7 mg, 0.018 mmol) and DPPB (7.7 mg, 0.018 mmol). The atmosphere was replaced with N2, and an EtOH solution (0.03 M) of NaOH (6.0 mL, 0.18 mmol) and (E)-2-methyl-3-phenylprop-2-enal (E/Z = 99:1; 1.26 mL, 9.0 mmol) were then added. Hydrogen gas was initially introduced into the autoclave at a pressure of 1.0 MPa before being reduced to 0.1 MPa by carefully releasing the stop valve. After this procedure was repeated three times, H2 was introduced at 5.0 MPa and the solution was stirred at 50 ˚C for 16 h. Silica gel chromatography (Et2O-hexane = 1:1) after removal of the solvent gave (E)-2-methyl-3-phenyl-
prop-2-en-1-ol (1.32 g, 99%, E/Z = 99:1).