ISSN 1070-4272, Russian Journal of Applied Chemistry, 2015, Vol. 88, No. 12, pp. 2050−2055. © Pleiades Publishing, Ltd., 2015.
Pd-Catalyzed Oxidative Oleﬁ nation of Arenes
with Oleﬁ ns via C–H Activation: Retention
of the Leaving Group
, Xiaojiang Yang, Dingli Wang, and Yang Zhang
State Key Laboratory of Oil and Gas Reservoir, Geology, and Exploitation, Southwest Petroleum University,
Chengdu, 610500, P. R. China
Received November 26, 2015
Abstract—Pd-catalyzed direct oxidative olefination of arenes with olefins via C–H activation is described in the
absence of any chelating directing groups. For Pd-catalyzed oxidative coupling between arenes and allyl acetate,
it was observed the retention of the leaving group.
The text was submitted by the authors in English.
Heck–Mizoroki arylation of oleﬁ ns with aryl halides
and triﬂ ates is one of the most popular and most distinct
methods for the construction of vinylarene derivatives
[1, 2]. Although great progress has been made since the
Heck reaction was ﬁ rst discovered, it still suffers from
one major drawback: the production of salt waste .
Thus, it could not meet the demands of atom
economical, efﬁ cient, environmentally benign synthetic
methods. However, the dehydrogenative Heck reaction
(DHR) could solve this problem, since the arylation of
an oleﬁ n proceeds through direct C–H/C–H coupling .
Since DHR was ﬁ rst introduced in 1969 by Fujiwara and
Moritani, direct C–H activation and functionalization
have gained much attention by chemists. Mostly, Pd, Ru,
and Rh are found to be efﬁ cient catalysts in these C–H
activation processes. However, the use of ortho-directing
groups (DG) is almost always required to improve the
regioselectivity and efﬁ ciency of DHR, including imino,
carbonyl, amido, hydroxyl, and 2-subsituted pyridyl
group (Scheme 1a) [5–8]. This restriction has greatly
limited the structural diversity of the products and
subsequent application to complex molecule synthesis,
since the directing group will become part of the product.
Only a few non-chelate assisted cases have been reported
[9–12], and these are limited to activiated C–H positions
of some speciﬁ c heterocylic structures. Although the
direct oxidative coupling reaction between benzene and
alkenes catalyzed by Pd complexes has been reported, this
catalytic system was limited to a few election-rich arenes
(Scheme 1b) [13–15]. Recently, Feng and Loh have
reported an example of oxidant-free Rh(III)-catalyzed
direct C–H olefination of arenes with allyl acetates
using N,N-disubstituted aminocarbonyl as DG . As
expected, this transformation involves β-elimination,
which was observed in many Pd-catalyzed Heck reactions
. Considering that the resulting substituted allylic
esters could be amenable to further functional-group
transformations, herein we demonstrate a highly efﬁ cient
Pd-catalyzed DHR of arenes with allyl actetate by
avoiding β-acetate or β-carbonate elimination under non-
chelate-assisted conditions [18–22]. Furthermore, this
catalytic protocol could be applied for DHR of acrylates
and styrenes as shown in Scheme 1.
In the course of our study on the oxidative coupling
of arenes with alkenes, we found an effective catalytic
system for the direct oxidative coupling of arenes that
contained no directing groups with acrylates. In this
O were used as
the catalysts, Ag
O was used as oxidant, and LiCl was
used as an additive.