The regioselective and diastereoselective allylic amination of allylic polybenzyl ethers using chlorosulfonyl isocyanate(CSI) are powerful methods for the preparation of a-amino-�-hydroxy acids and five or six-membered heterocycle compounds. These reactions have been used as key transformations for the syntheses of natural products such as (-)-lentiginosine, DAB, DGDP, deoxoprosophylline and deoxynojirimycin analogues.Valienamine is an ?-glucosidase inhibitor that was first isolated from the microbial degradation of validoxyamine A with Pseudomonas denitrificans in 1972. Later, it was produced from the degradation of validoxylamine A with Flavobacterium saccharophilum or from the NBS cleavage of validoxylamine A or its derivatives. Valienamine has been found to be a key component for biological activities in pseudo-aminosugars and pseudo oligosaccharides, which exhibit stronger enzyme inhibitory activities than valienamine itself, such as validamycins, acarbose, amylostatins, adiposins, acarviosin, and trestatins.Nowadays, we developed a new CSI reaction in the allylic ring systems and various cyclic allylic ethers and cyclic benzylic ethers were converted into the corresponding N-alkylcabamates using chlorosulfonyl isocyanate.Herein we report a short and efficient synthesis of Valienamine. The syntheses of the title compound was, accomplished in 13 steps from commercially available material and the key steps in the route involve asymmetric reduction using L-selectride and stereoselective introduction of N-Cbz group in the ring systems using the chlorosulfonyl isocyanate reaction.

Efficient total synthesis of valienamine via CSI-mediated stereoselective amination

241st National Meeting (2011)

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