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With the ever-increasing scope of organocuprates, a well-established Gilman reagent has been considered as an unprecedented synthetic tool in modern organic chemistry. The broad research profile of the Gilman reagent (RCuLi in THF or EtO) is owing to its propensity to carry out three kinds of reactions, , epoxide ring opening reactions, 1,4-conjugate addition reactions, and S2 reactions in a regioselective manner. This review examines the applications of Gilman reagent in the total synthesis of both abundant and scarce natural products of remarkable synthetic pharmaceutical profile reported since 2011.

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