10.1002/anie.201905905
Angewandte Chemie International Edition
RESEARCH ARTICLE
the Pd(0) species A was generated from Pd2dba3 and SOP,
Pd(II)-H species B was then afforded via oxidative addition of
Pd(0) to p-TsOH, Pd(II)-H species26 B coordinate with styrene to
Keywords: Pd-catalyzed • SOP ligand • enatioselectivity •
thiocarbonylation • styrenes
furnish
complex C. The insertion of Pd(II)-H to styrene with
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Scheme 7. Proposed catalytic cycle.
Conclusion
In summary,
a
highly enantioselective Pd-catalyzed
thiocarbonylation of styrenes using sulfoxide (P-dialkyl)-
phosphine (SOP) ligand under mild reaction conditions was
developed. Broad substrate scope, functional group tolerance,
expedient intermediates and the utility of late-stagy modification
of bioactive compounds were demonstrated. Primary mechanism
was investigated via kinetic studies, 31P-NMR analysis,
deuterium-labeling studies and DFT calculation. Further, a
plausible catalysis cycle was proposed. Further studies toward
extending this chemistry to other challenging alkenes are
currently underway.
Acknowledgements
We thank the National Nature Science Foundation of China (No.
21871251, 21572218 and 21472184), the Biological Resources
Programme, Chinese Academy of Sciences (KFJ-BRP-008) and
Sichuan Sci&Tech Department (2016JZ0022) for financial
support.
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