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 (R2CuLi in THF or Et2O) is owing to its propensity to carry out three kinds of reactions, i.e., epoxide ring opening reactions, 1,4-conjugate addition reactions, and SN2 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. The presented insights will be of a vital roadmap to general organic synthesis and it will contribute to the development of new natural products and their analogues in future drug discovery.
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