An Enantioselective Synthesis of N-Methylfucosamine via Tandem C‒C/C‒O Bond Formation

Dalibor Sames; Robin Polt

doi:10.1021/jo00095a039

An Enantioselective Synthesis of N-Methylfucosamine via Tandem C‒C/C‒O Bond Formation

Dalibor Sames, Robin Polt

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Abstract

Optically pure d-(+)-N-methylfucosamine (8) has been synthesized from a TBDMS-protected methyl l-serinate benzophenone Schiff base (O'Donnell's Schiff base, 1) in seven steps in 13% overall yield; Efficient construction of the requisite amino triol acetate 3a with the proper stereochemical configuration is accomplished in two steps with a chelation-controlled reduction-alkylation reaction using Bu₂AlH·Al-iBu₃/E-LiCH=CHCH₃, followed by oxidation with OsO₄. Conversion of the Schiff base to the N-benzhydryl protecting group and methylation (Eschweiler-Clark) is accomplished in one pot with NaCNBH₃ in the presence of H₂C=O. Deprotection and oxidation of the primary alcohol, followed by deacetylation with KCN, provided the desired product 8.

Original language	English (US)
Pages (from-to)	4596-4601
Number of pages	6
Journal	Journal of Organic Chemistry
Volume	59
Issue number	16
DOIs	https://doi.org/10.1021/jo00095a039
State	Published - Aug 1 1994

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Organic Chemistry

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title = "An Enantioselective Synthesis of N-Methylfucosamine via Tandem C‒C/C‒O Bond Formation",

abstract = "Optically pure d-(+)-N-methylfucosamine (8) has been synthesized from a TBDMS-protected methyl l-serinate benzophenone Schiff base (O'Donnell's Schiff base, 1) in seven steps in 13% overall yield; Efficient construction of the requisite amino triol acetate 3a with the proper stereochemical configuration is accomplished in two steps with a chelation-controlled reduction-alkylation reaction using Bu2AlH·Al-iBu3/E-LiCH=CHCH3, followed by oxidation with OsO4. Conversion of the Schiff base to the N-benzhydryl protecting group and methylation (Eschweiler-Clark) is accomplished in one pot with NaCNBH3 in the presence of H2C=O. Deprotection and oxidation of the primary alcohol, followed by deacetylation with KCN, provided the desired product 8.",

author = "Dalibor Sames and Robin Polt",

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T1 - An Enantioselective Synthesis of N-Methylfucosamine via Tandem C‒C/C‒O Bond Formation

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AU - Polt, Robin

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N2 - Optically pure d-(+)-N-methylfucosamine (8) has been synthesized from a TBDMS-protected methyl l-serinate benzophenone Schiff base (O'Donnell's Schiff base, 1) in seven steps in 13% overall yield; Efficient construction of the requisite amino triol acetate 3a with the proper stereochemical configuration is accomplished in two steps with a chelation-controlled reduction-alkylation reaction using Bu2AlH·Al-iBu3/E-LiCH=CHCH3, followed by oxidation with OsO4. Conversion of the Schiff base to the N-benzhydryl protecting group and methylation (Eschweiler-Clark) is accomplished in one pot with NaCNBH3 in the presence of H2C=O. Deprotection and oxidation of the primary alcohol, followed by deacetylation with KCN, provided the desired product 8.

AB - Optically pure d-(+)-N-methylfucosamine (8) has been synthesized from a TBDMS-protected methyl l-serinate benzophenone Schiff base (O'Donnell's Schiff base, 1) in seven steps in 13% overall yield; Efficient construction of the requisite amino triol acetate 3a with the proper stereochemical configuration is accomplished in two steps with a chelation-controlled reduction-alkylation reaction using Bu2AlH·Al-iBu3/E-LiCH=CHCH3, followed by oxidation with OsO4. Conversion of the Schiff base to the N-benzhydryl protecting group and methylation (Eschweiler-Clark) is accomplished in one pot with NaCNBH3 in the presence of H2C=O. Deprotection and oxidation of the primary alcohol, followed by deacetylation with KCN, provided the desired product 8.

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An Enantioselective Synthesis of N-Methylfucosamine via Tandem C‒C/C‒O Bond Formation

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