Structure-based rationalization of aldolase-catalyzed asymmetric synthesis

2002 ◽  
Vol 80 (6) ◽  
pp. 643-645 ◽  
Author(s):  
Junjie Liu ◽  
Grace DeSantis ◽  
Chi-Huey Wong
Keyword(s):  
Total Synthesis ◽  
Asymmetric Synthesis ◽  
Addition Reaction ◽  
Aldol Reaction ◽  
Wild Type ◽  
Asymmetric Aldol ◽  
Bonding Interaction ◽  
Aldol Addition

This paper describes a structure-based approach to elucidate the stereospecificity, including inversion of enantioselectivity, of the 2-deoxyribose-5-phosphate aldolase-catalyzed asymmetric aldol addition reaction using unnatural substrates designed for the total synthesis of epothilones. In addition, an aldolase variant with Ser-238 being altered for Asp was found to be 2.5 times more effective than the wild type in accepting the unphosphorylated substrate D-glyceraldehyde. A new H-bonding interaction between the Asp-238 carboxylate and the 3-hydroxyl of the substrate was identified and was used to rationalize the rate enhancements.Key words: aldol reaction, 2-deoxyribose-5-phosphate aldolase, mutagenesis, inversion of enantioselectivity.

Reagent control in the aldol addition reaction of chiral boron enolates with chiral aldehydes. Total synthesis of (3S,4S)-Statine

Tetrahedron ◽  
1997 ◽  
Vol 53 (15) ◽  
pp. 5593-5608 ◽  
Author(s):  
Cesare Gennari ◽  
Daniela Moresca ◽  
Anna Vulpetti ◽  
Gilles Pain
Keyword(s):  
Total Synthesis ◽  
Addition Reaction ◽  
Aldol Addition

scholarly journals Organocatalytic Asymmetric Aldol Reaction of Arylglyoxals and Hydroxyacetone: Enantioselective Synthesis of 2,3-Dihydroxy-1,4-diones

Molecules ◽  
2020 ◽  
Vol 25 (3) ◽  
pp. 648
Author(s):  
Yu-Hao Zhou ◽  
Yu-Zu Zhang ◽  
Zhu-Lian Wu ◽  
Tian Cai ◽  
Wei Wen ◽  
...  
Keyword(s):  
Primary Amine ◽  
Aldol Reaction ◽  
Enantioselective Synthesis ◽  
Asymmetric Aldol ◽  
Highly Efficient ◽  
Asymmetric Aldol Reaction ◽  
Aldol Addition ◽  
High Yields

A highly efficient quinine-derived primary-amine-catalyzed asymmetric aldol addition of hydroxyacetone to arylglyoxals is described. Structurally diverse anti-2,3-dihydroxy-1,4-diones were generated in high yields, with good diastereoselectivities and enantioselectivities.

Total synthesis of pipecolic acid and 1-C-alkyl 1,5-iminopentitol derivatives by way of stereoselective aldol reactions from (S)-isoserinal

2018 ◽  
Vol 16 (7) ◽  
pp. 1118-1125 ◽  
Author(s):  
Sebastian Baś ◽  
Rafał Kusy ◽  
Monika Pasternak-Suder ◽  
Cyril Nicolas ◽  
Jacek Mlynarski ◽  
...  
Keyword(s):  
Total Synthesis ◽  
Asymmetric Synthesis ◽  
Pipecolic Acid ◽  
Aldol Reactions ◽  
Aldol Addition

Asymmetric synthesis of the iminosugar moietyviadiastereoselective aldol addition of a pyruvate, a range of hydroxyketones and (S)-isoserinal, followed by catalytic reductive intramolecular amination.

Total Synthesis of Aculeatins A and B, and Formal Synthesis of Aculeatin D and 6-epi-Aculeatin D through an Asymmetric Aldol Reaction

Synthesis ◽  
2015 ◽  
Vol 47 (09) ◽  
pp. 1303-1308
Author(s):  
Xiaoji Wang ◽  
Shuangping Huang ◽  
Shipeng Chen ◽  
Gaopeng Wang ◽  
Jianting Zhang ◽  
...  
Keyword(s):  
Total Synthesis ◽  
Aldol Reaction ◽  
Asymmetric Aldol ◽  
Formal Synthesis ◽  
Asymmetric Aldol Reaction

Total Synthesis of Biselide A, A Cytotoxic Macrolide of Marine Origin

Synthesis ◽  
2017 ◽  
Vol 49 (13) ◽  
pp. 2958-2970 ◽  
Author(s):  
Ichiro Hayakawa ◽  
Hideo Kigoshi ◽  
Masami Okamura ◽  
Kazuaki Suzuki ◽  
Mami Shimanuki ◽  
...  
Keyword(s):  
Enzymatic Hydrolysis ◽  
Total Synthesis ◽  
Functional Group ◽  
Aldol Reaction ◽  
Oxygen Functional Group ◽  
Asymmetric Aldol ◽  
Marine Origin ◽  
Asymmetric Aldol Reaction ◽  
Cytotoxic Macrolide

The total synthesis of biselide A based on our earlier strategy of synthesizing haterumalides is reported. The highlights of this approach are the use of regioselective enzymatic hydrolysis for the installation of a C20 oxygen functional group and an asymmetric aldol reaction for the stereoselective introduction of a C3 oxygen functional group.

A concise asymmetric synthesis of (−)-trans-aerangis lactone

2018 ◽  
Vol 96 (12) ◽  
pp. 1061-1063 ◽  
Author(s):  
Rachana Pandey ◽  
Ranjana Prakash
Keyword(s):  
Ethylene Glycol ◽  
Total Synthesis ◽  
Asymmetric Synthesis ◽  
Aldol Reaction ◽  
Starting Material ◽  
Asymmetric Total Synthesis

A concise stereoselective approach to functionalized δ-lactone skeleton from monosilylated ethylene glycol as a starting material and its application to the asymmetric total synthesis of (−)-trans-aerangis lactone have been demonstrated. The synthesis utilizes the organocatalyzed MacMillan’s cross aldol reaction as a key step.

Carbon−Carbon Bond Formation

2008 ◽  
Author(s):  
Jie Jack Li ◽  
Chris Limberakis ◽  
Derek A. Pflum
Keyword(s):  
Natural Products ◽  
Asymmetric Synthesis ◽  
Aldol Condensation ◽  
Bond Formation ◽  
Aldol Reaction ◽  
Aldol Reactions ◽  
Academic Press ◽  
Carbon Carbon Bond ◽  
Stereogenic Centers ◽  
Aldol Addition

Reviews: (a) Vicarion, J. L.; Badia, D.; Carillo, L.; Reyes, E.; Etxebarria, J. Curr. Org. Chem. 2005, 9, 219-235. (b) Mahrwald, R. Ed. In Modern Aldol Reactions; Wiley-VCH: Weinheim, 2004; Vol. 1., pp. 1-335 (c) Mahrwald, R. Ed. In Modern Aldol Reactions; Wiley-VCH: Weinheim, 2004; Vol. 2., pp. 1-345.(d) Machajewski, T. D.; Wong, C.-H. Angew. Chem. Int. Ed. 2000, 39, 1352-1375. (e) Carriera, E. M. In Modern Carbonyl Chemistry; Otera, J.; Wiley-VCH: Weinheim, 2000; Chapter 8: Aldol Reaction: Methodology and Stereochemistry, 227-248. (f) Paterson, I.; Cowden, C. J.; Wallace, D. J. In Modern Carbonyl Chemistry; Otera, J.; Wiley-VCH: Weinheim, 2000; Chapter 9: Stereoselective Aldol Reactions in the Synthesis of Polyketide Natural Products, pp. 249-298. (g) Franklin, A. S.; Paterson, I. Contemp. Org. Synth. 1994, 1 317-338. (h) Heathcock, C. H. In Asymmetric Synthesis; Morrison, J. D., Ed.; Academic Press: Orlando, Fl.; 1984; Vol. 3., Chapter 2: The Aldol Addition Reaction, pp. 111-212. (i) Mukaiyama, T. Org. React. 1982, 28, 203-331. Since the early 1980s, aldol condensations involving boron enolates have gain great importance in asymmetric synthesis, particularly the synthesis of natural products with adjacent stereogenic centers bearing hydroxyl and methyl groups. (Z)-Boron enolates tend to give a high diastereoslectivity preference for the syn-stereochemistry while (E)-boron enolates favor the anti-stereochemistry. Because the B-O and B-C bonds are shorter than other metals with oxygen and carbon, the six membered Zimmerman–Traxler transition state in the aldol condensation tends to be more compact which accentuates steric interactions, thus leading to higher diastereoselectivity. When this feature is coupled with a boron enolate bearing a chiral auxillary, high enantioselectivity is achieved. Boron enolates are generated from a ketone and boron triflate in the presence of an organic base such as triethylamine. Reviews: (a) Abiko, A. Acc. Chem. Res. 2004, 37, 387-395. (b) Cowden, C. J. Org. React. 1997, 51, 1-200.

Current Progress in the Asymmetric Aldol Addition Reaction

ChemInform ◽  
2004 ◽  
Vol 35 (21) ◽  
Author(s):  
Claudio Palomo ◽  
Mikel Oiarbide ◽  
Jesus M. Garcia
Keyword(s):  
Addition Reaction ◽  
Asymmetric Aldol ◽  
Aldol Addition
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