Organic Letters
Letter
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generates intermediate III. This is followed by 1,6-conjugate
addition of 1a to III to form intermediate IV, which then
undergoes a proton-transfer process to give intermediate V.
Finally, intermediate V undergoes cyclization to furnish the
desired chroman derivative 3a with a terminal alkyne-
substituted quaternary carbon and releases the phosphine
catalyst.
In summary, we have disclosed a novel phosphine
sequentially catalyzed domino [4 + 2] cycloaddition of p-
QMs and α-substituted allenoates, affording a series of
chroman and tetrahydroquinoline derivatives bearing an
alkynyl-substituted quaternary carbon in high to excellent
yields. It is noteworthy that this is the first time that the α-
carbon and β′-carbon of α-substituted allenoates have
participated in the [4 + 2] cycloaddition. Both internal and
terminal alkynes could be constructed at the quaternary carbon
center of products. The newly constructed terminal alkynyl
group can be applied to the Sonogashira coupling and click
reaction. More mechanistic details and further work on the
asymmetric version of the present reaction are currently being
investigated by our group.
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ASSOCIATED CONTENT
* Supporting Information
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Experimental details, characterization data for new
compounds, copies of NMR spectra and X-ray crystal
Accession Codes
tallographic data for this paper. These data can be obtained
Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
AUTHOR INFORMATION
■
Corresponding Author
ORCID
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This work was financially supported by the National Natural
Science Foundation of China (21672109, 21472097, and
21871148) and the Natural Science Foundation of Tianjin
(15JCYBJC20000).
DEDICATION
■
Dedicated to 100th anniversary of Nankai University and
Dedicated to the 100th anniversary of the birth of Academician
Ruyu Chen.
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