Ti-Catalyzed
Radical Alkylation of Secondary and Tertiary
Alkyl Chlorides Using Michael Acceptors
Xiangyu Wu
Wei Hao
Ke-Yin Ye
Binyang Jiang
Gisselle Pombar
Zhidong Song
Song Lin
10.1021/jacs.8b08605.s002
https://acs.figshare.com/articles/dataset/Ti-Catalyzed_Radical_Alkylation_of_Secondary_and_Tertiary_Alkyl_Chlorides_Using_Michael_Acceptors/7256162
Alkyl
chlorides are common functional groups in synthetic organic
chemistry. However, the engagement of unactivated alkyl chlorides,
especially tertiary alkyl chlorides, in transition-metal-catalyzed
C–C bond formation remains challenging. Herein, we describe
the development of a Ti<sup>III</sup>-catalyzed radical addition of
2° and 3° alkyl chlorides to electron-deficient alkenes.
Mechanistic data are consistent with inner-sphere activation of the
C–Cl bond featuring Ti<sup>III</sup>-mediated Cl atom abstraction.
Evidence suggests that the active Ti<sup>III</sup> catalyst is generated
from the Ti<sup>IV</sup> precursor in a Lewis-acid-assisted electron
transfer process.
2018-10-10 00:00:00
Ti IV precursor
Cl atom abstraction
Ti-Catalyzed Radical Alkylation
Tertiary Alkyl Chlorides
Lewis-acid-assisted electron transfer process
Ti III
Michael Acceptors Alkyl chlorides
unactivated alkyl chlorides
Ti III catalyst
bond