Synthesis of (Z)-3,7-anhydro-1,2-dideoxy-2-deuterio-d-gluco-oct-2-enitol, a prochiral substrate for probing the catalytic functioning of glucosylases

Wolfgang Weiser, Jochen Lehmann, Curtis F. Brewer, Edward J. Hehre

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

Synthesis of the title compound provides a prochiral, glycosyl-donor substrate well suited for use as a probe of the catalytic functioning of d-glucosyl-mobilizing enzymes, because the full stereochemistry of enzymic reactions at its double bond may be unambiguously determined by examining the reaction products. The starting material for the synthesis was 2,6-anhydro-d-glycero-d-gulo-heptonic acid, from which 3,7-anhydro-4,5,6,8-tetra-O-benzyl-1-deoxy-d-glycero-d-gulo-2-octulose was prepared in eight steps. Reduction with lithium aluminum deuteride, and conversion of the resulting diastereomeric alcohols into (Z)-3,7-anhydro-4,5,6,8-tetra-O-benzyl-1,2-dideoxy-2-deuterio-d-gluco-oct-2-enitol (11) and 3,7-anhydro-4,5,6,8-tetra-O-benzyl-1,2-dideoxy-2-deuterio-d-glycero-d-gulo-oct-1-enitol (16), was carried out. By-products were 3,7-anhydro-2-O-benzoyl-4,5,6,8-tetra-O-benzyl-1,2-dideoxy-2-deuterio-d-erythro-l-galacto-octitol and 3,7-anhydro-2-O-benzoyl-4,5,6,8-tetra-O-benzyl-1,2-dideoxy-2-deuterio-d-erythro-l-talo-octitol, which could, like compound 16, be recycled. On debenzylation the oct-2-enitol 11 yielded (Z)-3,7-anhydro-1,2-dideoxy-2-deuterio-d-gluco-oct-2-enitol.

Original languageEnglish (US)
Pages (from-to)287-299
Number of pages13
JournalCarbohydrate Research
Volume183
Issue number2
DOIs
StatePublished - Dec 1 1988

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Mustelidae
Stereochemistry
Substrates
Aluminum
Reaction products
Lithium
Byproducts
Alcohols
Acids
Enzymes

ASJC Scopus subject areas

  • Biochemistry
  • Molecular Biology
  • Organic Chemistry

Cite this

Synthesis of (Z)-3,7-anhydro-1,2-dideoxy-2-deuterio-d-gluco-oct-2-enitol, a prochiral substrate for probing the catalytic functioning of glucosylases. / Weiser, Wolfgang; Lehmann, Jochen; Brewer, Curtis F.; Hehre, Edward J.

In: Carbohydrate Research, Vol. 183, No. 2, 01.12.1988, p. 287-299.

Research output: Contribution to journalArticle

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abstract = "Synthesis of the title compound provides a prochiral, glycosyl-donor substrate well suited for use as a probe of the catalytic functioning of d-glucosyl-mobilizing enzymes, because the full stereochemistry of enzymic reactions at its double bond may be unambiguously determined by examining the reaction products. The starting material for the synthesis was 2,6-anhydro-d-glycero-d-gulo-heptonic acid, from which 3,7-anhydro-4,5,6,8-tetra-O-benzyl-1-deoxy-d-glycero-d-gulo-2-octulose was prepared in eight steps. Reduction with lithium aluminum deuteride, and conversion of the resulting diastereomeric alcohols into (Z)-3,7-anhydro-4,5,6,8-tetra-O-benzyl-1,2-dideoxy-2-deuterio-d-gluco-oct-2-enitol (11) and 3,7-anhydro-4,5,6,8-tetra-O-benzyl-1,2-dideoxy-2-deuterio-d-glycero-d-gulo-oct-1-enitol (16), was carried out. By-products were 3,7-anhydro-2-O-benzoyl-4,5,6,8-tetra-O-benzyl-1,2-dideoxy-2-deuterio-d-erythro-l-galacto-octitol and 3,7-anhydro-2-O-benzoyl-4,5,6,8-tetra-O-benzyl-1,2-dideoxy-2-deuterio-d-erythro-l-talo-octitol, which could, like compound 16, be recycled. On debenzylation the oct-2-enitol 11 yielded (Z)-3,7-anhydro-1,2-dideoxy-2-deuterio-d-gluco-oct-2-enitol.",
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N2 - Synthesis of the title compound provides a prochiral, glycosyl-donor substrate well suited for use as a probe of the catalytic functioning of d-glucosyl-mobilizing enzymes, because the full stereochemistry of enzymic reactions at its double bond may be unambiguously determined by examining the reaction products. The starting material for the synthesis was 2,6-anhydro-d-glycero-d-gulo-heptonic acid, from which 3,7-anhydro-4,5,6,8-tetra-O-benzyl-1-deoxy-d-glycero-d-gulo-2-octulose was prepared in eight steps. Reduction with lithium aluminum deuteride, and conversion of the resulting diastereomeric alcohols into (Z)-3,7-anhydro-4,5,6,8-tetra-O-benzyl-1,2-dideoxy-2-deuterio-d-gluco-oct-2-enitol (11) and 3,7-anhydro-4,5,6,8-tetra-O-benzyl-1,2-dideoxy-2-deuterio-d-glycero-d-gulo-oct-1-enitol (16), was carried out. By-products were 3,7-anhydro-2-O-benzoyl-4,5,6,8-tetra-O-benzyl-1,2-dideoxy-2-deuterio-d-erythro-l-galacto-octitol and 3,7-anhydro-2-O-benzoyl-4,5,6,8-tetra-O-benzyl-1,2-dideoxy-2-deuterio-d-erythro-l-talo-octitol, which could, like compound 16, be recycled. On debenzylation the oct-2-enitol 11 yielded (Z)-3,7-anhydro-1,2-dideoxy-2-deuterio-d-gluco-oct-2-enitol.

AB - Synthesis of the title compound provides a prochiral, glycosyl-donor substrate well suited for use as a probe of the catalytic functioning of d-glucosyl-mobilizing enzymes, because the full stereochemistry of enzymic reactions at its double bond may be unambiguously determined by examining the reaction products. The starting material for the synthesis was 2,6-anhydro-d-glycero-d-gulo-heptonic acid, from which 3,7-anhydro-4,5,6,8-tetra-O-benzyl-1-deoxy-d-glycero-d-gulo-2-octulose was prepared in eight steps. Reduction with lithium aluminum deuteride, and conversion of the resulting diastereomeric alcohols into (Z)-3,7-anhydro-4,5,6,8-tetra-O-benzyl-1,2-dideoxy-2-deuterio-d-gluco-oct-2-enitol (11) and 3,7-anhydro-4,5,6,8-tetra-O-benzyl-1,2-dideoxy-2-deuterio-d-glycero-d-gulo-oct-1-enitol (16), was carried out. By-products were 3,7-anhydro-2-O-benzoyl-4,5,6,8-tetra-O-benzyl-1,2-dideoxy-2-deuterio-d-erythro-l-galacto-octitol and 3,7-anhydro-2-O-benzoyl-4,5,6,8-tetra-O-benzyl-1,2-dideoxy-2-deuterio-d-erythro-l-talo-octitol, which could, like compound 16, be recycled. On debenzylation the oct-2-enitol 11 yielded (Z)-3,7-anhydro-1,2-dideoxy-2-deuterio-d-gluco-oct-2-enitol.

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