Nickel-Catalyzed Homoallylation of Aldehydes in the Presence of Water and Alcohols

✍ Scribed by Masanari Kimura; Akihiro Ezoe; Shuji Tanaka; Yoshinao Tamaru

• Publisher: John Wiley and Sons
• Year: 2001
• Tongue: English
• Weight: 94 KB
• Volume: 113
• Category: Article
• ISSN: 0044-8249
• DOI: 10.1002/1521-3757(20011001)113:19<3712::aid-ange3712>3.0.co;2-t

✦ Synopsis

By virtue of their high polarity, a wide variety of allylic metal and metalloid (e.g., B, Si, Sn) complexes can serve as nucleophilic reagents toward carbonyl compounds; [1] some allylations can be successfully performed even in the presence of water under Barbier conditions. [2] On the other hand, because of their low polarity, the homoallylic metals that are capable of undergoing a nucleophilic addition reaction are likely to be limited to some electropositive main group metals (e.g., Li, Mg). [3] Accordingly, reactions with these homoallylic metals should be performed with care under strictly waterfree conditions and could be applied effectively to those compounds that do not possess an acidic hydrogen.

Here, we disclose that even in the presence of water and alcohols, nickel complexes serve as a catalyst to promote homoallylation of aldehydes with 1,3-dienes. The reaction proceeds under essentially the same conditions as those reported recently from these laboratories for a nickelcatalyzed homoallylation of carbonyl compounds with dienes in the presence of a stoichiometric amount of Et 3 B. [4±6] These two reactions, that is, in the presence and in the absence of water, provide bishomoallyl alcohols in comparable yields [6] a) C. M.