Asymmetric α-Alkylation of Acyclic Ketones Utilizing Chiral Nonracemic N-Amino Cyclic Carbamate Hydrazones

Date

2017-12

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Abstract

Asymmetric variants of ketone α-alkylation are highly important given that numerous natural products, drugs, and related compounds exist as α-functionalized ketone or derivatives thereof. A method for asymmetric α-alkylation of ketones using N-Amino cyclic carbamate (ACC) chiral auxiliaries is described. ACC alkylation delivers excellent stereoselectivity and yields, with a camphor-derived ACC auxiliary exhibits the highest stereoselectivities. A full account of this ACC method is discussed herein, including the synthesis of camphor-derived ACC auxiliaries, an amination method for preparation of ACC auxiliaries from commercially available oxazolidinones, and the study of the regioselectivity and diastereoselectivity of ACC hydrazone alkylation to determine factors compromising the selectivities.

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Keywords

ACC auxiliary, Ketone alpha alkylation, Azaenolate, Enantioselective, Asymmetric, Carbon–carbon bond formation, Amination, Monochloramine

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