Green Chemistry
Page 4 of 5
Green Chemistry
DOI: 10.1039/C7GC03665E
very efficient in the presence of either a Brønsted acid such as alkenes through a combined acid catalytic system. This
TfOH, or a Lewis acid such as Ga(OTf)3; on the contrary, no strategy worked well for challenging monosubstituted alkenes,
desired product was generated without an acid promoter. and exhibited good regioselectivity and functional group
Meanwhile, a KIE of 1.33 was obtained when Ga(OTf)3 was tolerance.
A
kinetic study suggested
a
sequential
used as promoter (Scheme S2 in Supporting Information), a acetylation/chlorination pathway.
result that is consistent with the assumption that the addition
Conflicts of interest
of AcOH to alkene was the rate-determining step; 2) the
nucleophilic substitution of 1-phenylethyl acetate with There are no conflicts interest to declare.
chloride afforded (1-chloroethyl)benzene (Scheme 2D). It was
Acknowledgements
found that the presence of acetic acid significantly facilitated
the substitution process due to the enhanced leaving group We are grateful to the National Institutes of Health for
capacity of the acetoxy group. Moreover, an inverse kinetic financial support (R01GM121660). Bo Xu is grateful to the
isotope effect (KIE=0.59) was observed (Scheme S3 in National Science Foundation of China for financial support
Supporting Information), which indicated a rehybridization of (NSFC-21472018).
the transition state involved in the substitution mechanism.11
In summary, we have developed a highly efficient and widely
applicable metal-free protocol for the hydrochlorination of
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