Observation of 1,3-Diketones Formation in the Reaction of Bulky Acyl Chlorides with Methyllithium 英文参考文献.docVIP

Molecules 2012, 17, 6415-6423; doi:10.3390/moleculeOPEN ACCESS molecules ISSN 1420-3049 /journal/molecules Article Observation of 1,3-Diketones Formation in the Reaction of Bulky Acyl Chlorides with Methyllithium Jian Zhang, Nianfa Yang * and Liwen Yang * Key Laboratory of Environmentally Friendly Chemistry and Applications of the Ministry of Education, College of Chemistry, Xiangtan University, Xiangtan 411105, China; E-Mail: zhangjian.507@163.com * Authors to whom correspondence should be addressed; E-Mails: nfyang@ (N.Y.); yangliwen_0519@163.com (L.Y.); Tel.: +86-731-5829-3833 (N.Y.); Fax: +86-731-5829-2251 (N.Y.). Received: 26 March 2012; in revised form: 23 May 2012 / Accepted: 23 May 2012 / Published: 29 May 2012 Abstract: The formation of 1,3-diketones was observed in the reactions of bulky acyl chlorides with methyllithium. The reaction products depend on the steric hindrance around the carbonyl group of the acyl chloride and the electronic effect of the group(s) linked to the carbonyl. When the steric hindrance around the carbonyl group of the acyl chloride is big enough, the 1,3-diketone is the only product. In the case of the moderate hindrance around the carbonyl group of the acyl chloride, a moderate yield of 1,3-diketone is obtained and some tertiary alcohol is generated. When there is no steric hindrance around the carbonyl group of the acyl chloride, the tertiary alcohol is the only product. When the steric hindrance around the carbonyl group is moderate and an electron-donating group is connected to the carbonyl of the acyl chloride, all three products—ketone, 1,3-diketone and tertiary alcohol—can be isolated from the reaction mixture after long reaction times. Keywords: acyl chloride; menthylformyl; methyllithium; C2-symmetric; 1,3-diketone 1. Introduction It is well known that the reaction of acyl chlorides with alkyllithiums produces a tertiary alcohol [1]. A ketone is obtaine