10.1002/anie.202101517
Angewandte Chemie International Edition
COMMUNICATION
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With these information, we propose a reasonable catalytic
pathway as illustrated in Scheme 5a. Mono-oxidation of diol and
imine condensation (leading to II) is followed by a facile Heyns
Rearrangement to yield III. A second imine condensation yields
the key amino imine IV, which undergoes reduction by the metal
hydride to deliver the desired diamine with regeneration of
catalyst. Overall, one redox cycle is coupled with two
condensation and one isomerization to realize an efficient
double amination of diols. For the enantioselective variant, we
propose that the reaction likely proceeds through a dynamic
kinetric asymmetric transformation similar to our previous
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reported examples (Scheme 5b).[12b-c] Although
a direct
enantioselective reduction of ketimine IV to produce 6 (Pathway
A) cannot be completely ruled out, we believe it is relatively
sluggish compared to the tautomerization to enamine V and then
VI/VI‘. In that case, a catalyst-controlled selective reduction of VI
in preference over VI‘ then lead to enantioenriched vicinal
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diamine synthesis through
a dynamic kinetic asymmetric
transformation (Pathway B).
In conclusion, we have achieved an unprecedented diastereo-
and enantioconvergent synthesis of diamines from simple diols
using anilines. These transformations proceed through a redox-
neutral process with high atom- and step-econony, employ
simple Ru- or Ir-based catalysts in combination with Lewis or
Bronsted acid co-catalyst, and deliver highly valuable
enantioenriched vicinal diamines. Further investigation will be
focused on the development more efficient catalytic borrowing
hydrogen systems to address simultaneous control of
contiguous stereocenters for the access to a wider range of
enantiopure vicinal diamines and other valuable poly-
functionalized compounds.
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Acknowledgements
We are grateful for the financial support from the Ministry of
Education of Singapore (R-143-000-A94-112) and National
University of Singapore (R-143-000-A57-114) to Y.Z., and the
National Science Foundation of China (32001266) to Y.L.
[9]
Keywords: chiral diamines • redox-neutral • double amination of
diols • cooperative catalysis • enantioselectivity
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5
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