Synthesis of 3-Deoxy-D-manno-2-octulosonic acid (KDO) and its analogs based on KDO aldolase-catalyzed reactions

Takeshi Sugai, Gwo Jenn Shen, Yoshitaka Ichikawa, Chi Huey Wong

Research output: Contribution to journalArticle

95 Citations (Scopus)

Abstract

3-Deoxy-D-manno-2-octulosonic acid (D-KDO) was synthesized from D-arabinose and pyruvate in 67% yield by using KDO aldolase (EC 4.1.2.23) from Aureobacterium barkerei strain KDO-37-2 (ATCC 49977). Studies or, he substrate specificity of the enzyme with more than 20 natural and unnatural sugars indicate that this enzyme widely accepts trioses, tetroses, pentoses and hexoses as substrates, especially the ones with the R configuration at the 3 position. The substituent on the 2 position had little effect on the aldol reaction. Nine substrates were submitted to the adol reaction to prepare the products including D-KDO, 3-deoxy-D-arabino-2-heptulosonic acid (D-DAH), 2-keto-3-deoxy-L-gluconic acid (L-KDG), and 3-deoxy-L-glycero-L-galacto-nanulosonic acid (D-KDN). It appears that the attack of pyruvate took p ace on re face of the carbonyl group of acceptor substrates, a facial selection complementary to sialic acid aldolase (si face attack) reactions. The adolase products can be converted to aldoses via radical-mediated decarboxylation. For example, decarboxylation of pentaacetyl-KDO and hexaacetylneuraminic acid gave penta-O-acetyl-2-deoxy-β-D-manno-heptose and penta-O-acetyl-4-acetamido-2,4-dideoxy-β-D-glaycero-D-galacto-octose, respectively.

Original languageEnglish
Pages (from-to)413-421
Number of pages9
JournalJournal of the American Chemical Society
Volume115
Issue number2
Publication statusPublished - 1993
Externally publishedYes

Fingerprint

Rubiaceae
Fructose-Bisphosphate Aldolase
Decarboxylation
N-acetylneuraminate lyase
Pyruvic Acid
Tetroses
Trioses
Heptoses
Pentoses
2,4-Dichlorophenoxyacetic Acid
Arabinose
Acids
Hexoses
Substrates
Enzymes
Substrate Specificity
Sugars
3-deoxy-manno-oct-2-ulopyranosonic acid
gluconic acid
3-deoxy-D-arabino-heptulosonate-7-phosphate

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Synthesis of 3-Deoxy-D-manno-2-octulosonic acid (KDO) and its analogs based on KDO aldolase-catalyzed reactions. / Sugai, Takeshi; Shen, Gwo Jenn; Ichikawa, Yoshitaka; Wong, Chi Huey.

In: Journal of the American Chemical Society, Vol. 115, No. 2, 1993, p. 413-421.

Research output: Contribution to journalArticle

@article{4dafeda7cd7d47a49c53e919419734d0,
title = "Synthesis of 3-Deoxy-D-manno-2-octulosonic acid (KDO) and its analogs based on KDO aldolase-catalyzed reactions",
abstract = "3-Deoxy-D-manno-2-octulosonic acid (D-KDO) was synthesized from D-arabinose and pyruvate in 67{\%} yield by using KDO aldolase (EC 4.1.2.23) from Aureobacterium barkerei strain KDO-37-2 (ATCC 49977). Studies or, he substrate specificity of the enzyme with more than 20 natural and unnatural sugars indicate that this enzyme widely accepts trioses, tetroses, pentoses and hexoses as substrates, especially the ones with the R configuration at the 3 position. The substituent on the 2 position had little effect on the aldol reaction. Nine substrates were submitted to the adol reaction to prepare the products including D-KDO, 3-deoxy-D-arabino-2-heptulosonic acid (D-DAH), 2-keto-3-deoxy-L-gluconic acid (L-KDG), and 3-deoxy-L-glycero-L-galacto-nanulosonic acid (D-KDN). It appears that the attack of pyruvate took p ace on re face of the carbonyl group of acceptor substrates, a facial selection complementary to sialic acid aldolase (si face attack) reactions. The adolase products can be converted to aldoses via radical-mediated decarboxylation. For example, decarboxylation of pentaacetyl-KDO and hexaacetylneuraminic acid gave penta-O-acetyl-2-deoxy-β-D-manno-heptose and penta-O-acetyl-4-acetamido-2,4-dideoxy-β-D-glaycero-D-galacto-octose, respectively.",
author = "Takeshi Sugai and Shen, {Gwo Jenn} and Yoshitaka Ichikawa and Wong, {Chi Huey}",
year = "1993",
language = "English",
volume = "115",
pages = "413--421",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "2",

}

TY - JOUR

T1 - Synthesis of 3-Deoxy-D-manno-2-octulosonic acid (KDO) and its analogs based on KDO aldolase-catalyzed reactions

AU - Sugai, Takeshi

AU - Shen, Gwo Jenn

AU - Ichikawa, Yoshitaka

AU - Wong, Chi Huey

PY - 1993

Y1 - 1993

N2 - 3-Deoxy-D-manno-2-octulosonic acid (D-KDO) was synthesized from D-arabinose and pyruvate in 67% yield by using KDO aldolase (EC 4.1.2.23) from Aureobacterium barkerei strain KDO-37-2 (ATCC 49977). Studies or, he substrate specificity of the enzyme with more than 20 natural and unnatural sugars indicate that this enzyme widely accepts trioses, tetroses, pentoses and hexoses as substrates, especially the ones with the R configuration at the 3 position. The substituent on the 2 position had little effect on the aldol reaction. Nine substrates were submitted to the adol reaction to prepare the products including D-KDO, 3-deoxy-D-arabino-2-heptulosonic acid (D-DAH), 2-keto-3-deoxy-L-gluconic acid (L-KDG), and 3-deoxy-L-glycero-L-galacto-nanulosonic acid (D-KDN). It appears that the attack of pyruvate took p ace on re face of the carbonyl group of acceptor substrates, a facial selection complementary to sialic acid aldolase (si face attack) reactions. The adolase products can be converted to aldoses via radical-mediated decarboxylation. For example, decarboxylation of pentaacetyl-KDO and hexaacetylneuraminic acid gave penta-O-acetyl-2-deoxy-β-D-manno-heptose and penta-O-acetyl-4-acetamido-2,4-dideoxy-β-D-glaycero-D-galacto-octose, respectively.

AB - 3-Deoxy-D-manno-2-octulosonic acid (D-KDO) was synthesized from D-arabinose and pyruvate in 67% yield by using KDO aldolase (EC 4.1.2.23) from Aureobacterium barkerei strain KDO-37-2 (ATCC 49977). Studies or, he substrate specificity of the enzyme with more than 20 natural and unnatural sugars indicate that this enzyme widely accepts trioses, tetroses, pentoses and hexoses as substrates, especially the ones with the R configuration at the 3 position. The substituent on the 2 position had little effect on the aldol reaction. Nine substrates were submitted to the adol reaction to prepare the products including D-KDO, 3-deoxy-D-arabino-2-heptulosonic acid (D-DAH), 2-keto-3-deoxy-L-gluconic acid (L-KDG), and 3-deoxy-L-glycero-L-galacto-nanulosonic acid (D-KDN). It appears that the attack of pyruvate took p ace on re face of the carbonyl group of acceptor substrates, a facial selection complementary to sialic acid aldolase (si face attack) reactions. The adolase products can be converted to aldoses via radical-mediated decarboxylation. For example, decarboxylation of pentaacetyl-KDO and hexaacetylneuraminic acid gave penta-O-acetyl-2-deoxy-β-D-manno-heptose and penta-O-acetyl-4-acetamido-2,4-dideoxy-β-D-glaycero-D-galacto-octose, respectively.

UR - http://www.scopus.com/inward/record.url?scp=0000984816&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0000984816&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:0000984816

VL - 115

SP - 413

EP - 421

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 2

ER -