10.1002/anie.202010740
Angewandte Chemie International Edition
RESEARCH ARTICLE
addition. In addition, (1R)E-TS2 is 2.1 kcal mol-1 lower than
(1R)Z-TS2, in agreement with the experimental observation that
the Py addition (step 2 in eq 3) proceeded faster than that (step
2 in eq 4) (2h versus 12h).
A remarkable feature of the reaction is the exclusive Z-
selectivity (Table 3). As detailed in Supporting Information, we
attribute the Z-selectivity of the reaction to the diastereoselective
Py addition and the cis-selective E1cB-elimination of IM6. With
the caution of using monomeric K2CO3 to model K2CO3 base
which may exist as aggregations in the solvent, we also
tentatively analyzed the origins of the Z-selectivity of the reaction
in the Supporting Information.
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Conclusion
In summary, α-C-H arylation of α,β-unsaturated nitriles with aryl
sulfoxides has been developed on the basis of a Morita-Baylis-
Hillman-type addition triggered [3,3]-rearrangement. The
reaction features high regio- and stereo-selectivity, excellent
functional-group compatibility, and broad substrate scope for
both coupling partners. The high efficiency of decagram-scale
reaction highlights the practicability of the method. In a word, the
protocol not only provides an efficient approach for the synthesis
of valuable α-aryl α,β-unsaturated nitriles but also demonstrates
the feasibility of merging MBH reaction into [3,3]-rearrangement
process that is expected to inspire the development of new
rearrangement reactions. The control experiments and DFT
calculations support a reaction sequence including the assembly
of Tf2O activated aryl sulfoxide with α,β-unsaturated nitrile to
give unsaturated imine-sulfoxonium salt, MBH-like 2-
chloropyridine addition to give α-aryl β-ammonium nitrile, [3,3]-
rearrangement to form C-C bond, and E1cB-elimination to give
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to the diastereoselective 2-chloropyridine addition and the cis-
selective E1cB-elimination.
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Acknowledgements
B. P. thanks the Key Laboratory of the Ministry of Education for
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(LR20B020001). Z.-X. W. acknowledges the support of NSFC-
21773240.
Keywords: [3,3]-sigmatropic rearrangement • Morita-Baylis-
Hillman reaction • electrophilic activation • sulfoxide • arylation
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