AbstractThe reaction of borane with α‐pinene in tetrahydrofuran attains equilibrium in 3 days at 0°. With 15% excess (+)‐α‐pinene ([α]D26.5+ 47.99°), the formation of diisopinocampheylborane is essentially quantitative (‐99.5%). The longer reaction time is accompanied by a selective incorporation of the major isomer into the reagent. Thus, (+)‐α‐pinene, dehydroborated from diisopinocampheylborane with triethylamine, exhibits an optical rotation of [α]D23.5+ 51.0°, indicating an optical purity of 99.8%, and the isopinocampheol, obtained following the oxidation of the reagent, showed [α]D23−35.1° (c10, benzene), a higher rotation than any realized previously. The hydroboration ofcis‐2‐butene with this diisopinocampheylborane in tetrahydrofuran at −25° provided 2‐butanol of high optical purity, [α]D22.5−13.29°, an optical purity of 98.4%. Thus this reaction proceeds with