Communication
ChemComm
(Grant no. XDB20000000), the National Natural Science Foun-
dation of China (21372250, 21121062, 21302203, 20732008,
21772037, 21772226, 21861132014 and 91956115), and the
Fundamental Research Funds for the Central Universities
222201717003.
Conflicts of interest
There are no conflicts of interest to declare.
Notes and references
Scheme 6 Proposed reaction mechanism.
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Scheme 7 Preliminary asymmetric studies and a scale-up synthesis.
The catalytic asymmetric version of this divergent cycloaddi-
tion was also investigated (see Table S1 in the ESI† for more
details) and we found that using L1 as a chiral phosphine
ligand could deliver 3a in 33% yield along with 31% ee
(Scheme 7a). Finally, a scale-up synthesis was performed with
5.0 mmol of substrate 1a and 2.5 mmol of substrate 2a under
both conditions A and B, affording the corresponding products
3a and 4a in 52% and 47% (dr: 7 : 1) yields, respectively
(Scheme 7b).
In summary, we have disclosed an efficient and convenient
synthetic protocol to produce spirooxindoles fused with a five or
six-membered ring by the reaction of vinylidenecyclopropane-
diesters with methyleneindolinones in the presence of palladium
catalyst and a Lewis acid. By simply switching the ligands, an
unprecedented zwitterionic p-propargyl palladium catalyzed regio-
divergent cyclization is realized to enable (3+2) and (4+2) cycload-
ditions. This discovery sheds light on the development of
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11 The relationship between the regioselectivity of palladium-catalyzed
diversity of its reaction mode. Further investigations on the
asymmetric version of this palladium-catalyzed divergent cycload-
dition and application of this protocol to the synthesis of biolo-
gically active substances are underway.
cyclization of propargylic carbonates and the biting angle of the
employed bidentate phosphine ligand has been reported:
D. S. Daniels, A. S. Jones, A. L. Thompson, R. S. Paton and
E. A. Anderson, Angew. Chem., Int. Ed., 2014, 53, 1915–1920.
We are grateful for the financial support from the Strategic
Priority Research Program of the Chinese Academy of Sciences 12 C. Fu and S. Ma, Org. Lett., 2005, 7, 1707–1709.
4786 | Chem. Commun., 2021, 57, 4783–4786
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