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Chiral Phosphoric Acid Catalyzed Asymmetric Synthesis of Hetero‐triarylmethanes from Racemic Indolyl Alcohols
Author(s) -
Yue Caizhen,
Na Fei,
Fang Xiantao,
Cao Yang,
Antilla Jon C.
Publication year - 2018
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201804330
Subject(s) - enantioselective synthesis , chemistry , phosphoric acid , catalysis , reactivity (psychology) , nucleophile , combinatorial chemistry , organocatalysis , organic chemistry , medicine , alternative medicine , pathology
The direct enantioselective 1,4‐ and 1,8‐arylations of 7‐methide‐7 H ‐indoles and 6‐methide‐6 H ‐indoles, respectively, generated in situ from diarylmethanols, with electron‐rich arenes as nucleophiles, has been achieved in the presence of chiral phosphoric acids (CPAs). These two remote activation protocols provide an efficient approach for the construction of diverse hetero‐triarylmethanes in high yields (up to 97 %) and with excellent enantioselectivities (up to 96 %). Mechanistically inspired experiments tentatively indicate that the catalytic enantioselective 1,4‐addition as well as the formal S N 1 substitution could proceed efficiently in the similar catalytic systems. Furthermore, the modification of the catalytic system and diarylmethanol structure successfully deviates the reactivity toward a remote, highly enantioselective 1,8‐arylation reaction. This flexible activation mode and novel reactivity of diarylmethanols expand the synthetic potential of chiral phosphoric acids.