- N-Methyl Allylic Amines from Allylic Alcohols by Mitsunobu Substitution Using N-Boc Ethyl Oxamate
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We report the practical, scalable synthesis of a range of N-methyl allylic amines. Primary and secondary allylic alcohols underwent a regioselective Mitsunobu reaction with readily accessible N-Boc ethyl oxamate to deliver the corresponding N-Boc allylic amines, including in enantiopure form via stereospecific substitution. Subsequent N-methylation and Boc deprotection without chromatography yielded the amine products as hydrochloride salts. This method solves the problem of converting commercially available alcohols into often volatile N-methyl allylic amines, many of which have limited commercial availability.
- Van Veen, Branca C.,Wales, Steven M.,Clayden, Jonathan
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p. 8538 - 8543
(2021/06/30)
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- Direct, intermodular, enantioselective, iridium-catalyzed allylation of carbamates to form carbamate-protected, branched allylic amines
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The direct reaction between carbamates and achiral allylic carbonates to form branched, conveniently protected primary allylic amines with high regioseiectivity and enantioselectivity Is reported. This process occurs without base or with 0.5 equiv K3PO4 In the presence of a metalacyclic iridium catalyst containing a labile ethylene ligand. The reactions of aryl-, heteroaryl-, and alkyl-substituted allylic carbonates with BocNH 2, FmocNH2, CbZNH2, TrocNH2, TeocNH2, and 2-oxazolidinone occur In good yields, with high selectivity for the branched isomer and high enantioselectivities (98% average ee).
- Weix, Daniel J.,Markovic, Dean,Ueda, Mitsuhiro,Hartwig, John F.
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supporting information; experimental part
p. 2944 - 2947
(2009/12/05)
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