Lin Zhiyang, Lan Yun, Wang Chuan
Hefei National Laboratory for Physical Science at the Microscale and Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, P. R. China.
Center for Excellence in Molecular Synthesis of CAS, Hefei, Anhui 230026, P. R. China.
Org Lett. 2020 May 1;22(9):3509-3514. doi: 10.1021/acs.orglett.0c00960. Epub 2020 Apr 10.
Herein, we report a method for efficient synthesis of -difluorobishomoallylic alcohols starting from trifluoromethyl-substituted alkenes and epoxides via a titanocene-catalyzed reductive domino reaction, which consists of a Ti(III)-mediated radical-type ring opening and the following allylic defluorinative cross-coupling reaction via sequential radical addition and β-F elimination. Notably, complete regioselectivity and high tolerance of functionalities can be achieved in this reaction. Furthermore, diverse 6-fluoro-3,4-dihydro-2-pyrans have been prepared through derivatization of the cross-coupling products in one single step.
在此，我们报道了一种从三氟甲基取代的烯烃和环氧化物出发，通过钛茂催化的还原多米诺反应高效合成α-二氟高烯丙醇的方法，该反应由Ti(III)介导的自由基型开环反应以及随后通过连续自由基加成和β-F消除进行的烯丙基脱氟交叉偶联反应组成。值得注意的是，该反应能够实现完全的区域选择性和对官能团的高耐受性。此外，通过一步衍生化交叉偶联产物，制备了多种6-氟-3,4-二氢-2-吡喃。
