Low-temperature n-butyllithium-induced rearrangement of allyl 1,1-dichlorovinyl ethers
Low-temperature n-butyllithium-induced rearrangement of allyl 1,1-dichlorovinyl ethers
复制标题
DOI：
10.1021/ol052685j
复制
发表时间：
2006-02-02
期刊：
影响因子：
5.2
通讯作者：
Minehan, T
中科院分区：
文献类型：
--
作者：
Christopher, A;Brandes, D;Minehan, T
在低温下用n-BuLi处理时，各种烯丙基1，1-二氯乙烯基醚2在醇加成后经历重排以提供γ，δ-不饱和酯3。利用该方案，可以在温和条件下以高产率形成含有季中心的化合物（3e：R-1 = H-1 R-2，R-3 = -（CH 2）（5）-; 3f：R-1 = H，R-2 = CH 3，R-3 =（CH 2）（2）CH（CH 3）（2））。该反应是立体特异性的，可用于制备δ（2，3）-β-C-糖苷和α，β-二取代内酯。
Upon treatment with n-BuLi at low temperatures, a variety of allyl 1,1-dichlorovinyl ethers 2 undergo rearrangement to furnish gamma,delta-unsaturated esters 3 after alcohol addition. Compounds containing quaternary centers (3e: R-1 = H-1 R-2, R-3 = -(CH2)(5)-; 3f: R-1 = H, R-2 = CH3, R-3 = (CH2)(2)CH(CH3)(2)) may be formed in high yield and under mild conditions utilizing this protocol. The reaction is stereospecific and may be applied to the preparation of Delta(2,3)-beta-C-glycosides and alpha,beta-disubstituted lactones.