Department of Chemistry, Princeton University, Princeton, New Jersey 08544, USA.
J Am Chem Soc. 2010 Dec 15;132(49):17402-4. doi: 10.1021/ja109120n. Epub 2010 Nov 18.
The enantioselective fluorination of readily available cyclic allylic chlorides with AgF has been accomplished using a Pd(0) catalyst and Trost bisphosphine ligand. The reactions proceed with unprecedented ease of operation for Pd-mediated nucleophilic fluorination, allowing access to highly enantioenriched cyclic allylic fluorides that bear diverse functional groups. Evidence that supports a mechanism in which C-F bond formation occurs by an S(N)2-type attack of fluoride on a Pd(II)-allyl intermediate is presented.
使用 Pd(0)催化剂和 Trost 双膦配体，已经实现了通过 AgF 对易得的环状烯丙基氯的对映选择性氟化。该反应具有 Pd 介导的亲核氟化前所未有的操作简便性，允许获得高对映富集的环状烯丙基氟化物，这些氟化物具有多种官能团。提出了一种支持 C-F 键形成是通过氟化物对 Pd(II)-烯丙基中间体的 S(N)2 型进攻的机制的证据。
