Bao Hongli, Bayeh Liela, Tambar Uttam K
Department of Biochemistry, The University of Texas, Southwestern Medical Center at Dallas, 5323 Harry Hines Boulevard, Dallas, TX 75390-9038 (USA) http://www4.utsouthwestern.edu/tambarlab/
Angew Chem Int Ed Engl. 2014 Feb 3;53(6):1664-8. doi: 10.1002/anie.201309134. Epub 2014 Jan 23.
New advances in the functionalization of unactivated olefins with carbon nucleophiles have provided more efficient and practical approaches to convert inexpensive starting materials into valuable products. Recent examples have been reported with stabilized carbon nucleophiles, tethered carbon nucleophiles, diazoesters, and trifluoromethane donors. A general method for functionalizing olefins with aromatic, aliphatic, and vinyl Grignard reagents was developed. In a one-pot process, olefins are oxidized by a commercially available reagent to allylic electrophiles, which undergo selective copper-catalyzed allylic alkylation with Grignard reagents. Products are formed in high yield and with high regioselectivity. This was utilized to synthesize a series of skipped dienes, a class of compounds that are prevalent in natural products and are difficult to synthesize by known allylic alkylation methods.
未活化烯烃与碳亲核试剂官能团化的新进展为将廉价起始原料转化为有价值的产品提供了更高效、实用的方法。最近有使用稳定化碳亲核试剂、 tethered碳亲核试剂、重氮酯和三氟甲烷供体的相关报道。已开发出一种用芳基、脂肪族和乙烯基格氏试剂对烯烃进行官能团化的通用方法。在一锅法过程中，烯烃被一种市售试剂氧化为烯丙基亲电试剂，其与格氏试剂进行选择性铜催化的烯丙基烷基化反应。产物以高收率和高区域选择性形成。这被用于合成一系列间隔二烯，这类化合物在天然产物中普遍存在且难以通过已知的烯丙基烷基化方法合成。
