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The chiral indole is an important structure in organic chemistry. We have developed an enantioselective hydrogen transfer reaction of indolylmethanol, which is characterized by the combined use of benzothiazoline and a newly synthesized chiral phosphoric acid. The reaction furnished indoles bearing a chiral tertiary carbon center at the 3-position in high to excellent yields and with excellent enantioselectivities, most of which are greater than 95% ee. The chiral indole was converted into an inhibitor of leukotriene production while ret