10.1002/anie.201804330
Angewandte Chemie International Edition
COMMUNICATION
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Scheme 6. The mechanistic investigation for the 1,8-addition reaction.
Finally, to further demonstrate the practicality of this remote
strategy, the reaction of 7-indolylmethanl 1a with indole 2a was
performed at one-gram scale with the standard conditions (Scheme
7). To our delight, the corresponding product 3a was successfully
obtained with slightly decreased yield and maintained
enantioselectivity, which illustrates the practical application value of
this enantioselective transformation.
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Scheme 7. Gram-scale preparation of 3a.
In conclusion, we have demonstrated the possibility to switch
the reaction patterns and activation modes of designed
diarylmethanols by means of CPA catalysis. The asymmetric
transformation of 7-indolylmethanol features
a broad substrate
scope, low catalyst loading and flexible activation mode, providing
an efficient and broadly applicable method for asymmetric synthesis
of hetero-triarylmethanes. Moreover, the 1,4-addition reaction was
further extended to include the remote 1,8-addition reaction with
excellent yield and enantioselectivity. Control experiments provided
important insights into the reaction mechanism. Interestingly, a
mono-activation mode might be involved in this process, though not
completely definitive without further experiments. Further expansion
and application of diarylmethanols are currently under investigation
in our laboratory and will be reported in due course.
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Keywords:
enantioselective
catalysis•1,4-addition•1,8-addition
•remote enantiocontrol•mono activation• chiral phosphoric acids
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