Journal of the American Chemical Society
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(Chloroethynyl)arenes and phenyl chloroethynyl sulfide
are demonstrated as effective alkyne partners, with the
latter leading to generally more efficient reactions. The
salient feature of these reactions is the scope of alkenes,
which are all electronically unactivated and hence
challenging. They range from various disubstituted alkenes
to mono-substituted alkenes. In comparison, the prior arts
in gold catalysis have demonstrated only one success with
cyclooctene and none with mono-substituted unactivated
alkenes. In addition, the reactions with mono-substituted
alkenes exhibit excellent regioselectivities, which are
markedly better than those reported in scarce literature
precedents promoted/catalyzed by other metals. With 1,2-
disubstituted unactivated alkenes, the reactions are largely
stereospecific. The cyclobutene products can be prepared
in nearly gram scale and readily undergo further
transformations including various cross-coupling reactions
involving the C(sp2)-Cl and/or the C(sp2)-SPh bonds, which
in turn substantially broaden the scope of accessible
cyclobutene products and therefore notably enhance the
synthetic utility of of these bimolecular reactions.
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ASSOCIATED CONTENT
Supporting Information
Detailed experimental procedures, compound characterization
and X-ray diffraction data of 6f. This material is available free
AUTHOR INFORMATION
Corresponding Author
Present Addresses
I College of Chemical Engineering, AnHui University of Science
& Technology, Huainan 232001, P. R. China.
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II Key Laboratory of Bioorganic synthesis of Zhejiang University
of Technology, Hangzhou, Zhejiang 310014, China.
Notes
The authors declare no competing financial interests.
ACKNOWLEDGMENT
Y. Bai thanks China Scholarship Council for scholarship. We
thank NIGMS R01GM123342 for financial support and NIH
shared instrument grant S10OD012077 for the purchase of a
400 MHz NMR spectrometer.
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