10.1002/anie.201807881
Angewandte Chemie International Edition
COMMUNICATION
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we propose a plausible catalytic cycle (Scheme 4). Hydrogen
liberation from 3 forms complex 5 which undergoes O-H activation by
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complex 5 can reversibly add H2O/D2O (Scheme 3, c and SI).
In conclusion, unprecedented base-metal catalyzed direct
transformation of alcohols to alkenes by acceptorless
dehydrogenative coupling of alcohols with hydrazine, as well as
dehydrogenative coupling of alcohols with hydrazones to form mixed
alkenes is demonstrated. Moreover, the reaction is catalyzed by a
complex of an earth abundant metal (Mn). This E-alkene formation
proceeds in absence of added bases, or hydrogen acceptors, using
the manganese pincer catalyst (iPr-PNHP)Mn(H)(CO)2. A plausible
mechanism is provided, based on preparation of postulated
intermediates and demonstration of steps though to be involved in the
catalytic cycle, including N-H activation by amido-amine metal-ligand
cooperation.
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Acknowledgements
This research was supported by the European Research Council
(ERC AdG 692775), and by the Israel Science Foundation. U. K. D is
thankful to The Science & Engineering Research Board (SERB), Govt.
of India for the SERB Overseas Postdoctoral Fellowship.
Keywords: manganese pincer catalyst• dehydrogenative
coupling• alcohol• hydrazine • E-alkene
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