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.

Sequential Biocatalytic Aldol Reactions in Multistep Asymmetric Synthesis: Pipecolic Acid, Piperidine and Pyrrolidine (Homo)Iminocyclitol Derivatives from Achiral Building Blocks

2014 ◽  
Vol 356 (14-15) ◽  
pp. 3007-3024 ◽  
Author(s):  
Anna Soler ◽  
Xavier Garrabou ◽  
Karel Hernández ◽  
Mariana L. Gutiérrez ◽  
Eduardo Busto ◽  
...  
Keyword(s):  
Asymmetric Synthesis ◽  
Building Blocks ◽  
Pipecolic Acid ◽  
Aldol Reactions

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.

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.

ChemInform Abstract: Sequential Biocatalytic Aldol Reactions in Multistep Asymmetric Synthesis: Pipecolic Acid, Piperidine and Pyrrolidine (Homo)Iminocyclitol Derivatives from Achiral Building Blocks.

ChemInform ◽  
2015 ◽  
Vol 46 (15) ◽  
pp. no-no
Author(s):  
Anna Soler ◽  
Xavier Garrabou ◽  
Karel Hernandez ◽  
Mariana L. Gutierrez ◽  
Eduardo Busto ◽  
...  
Keyword(s):  
Asymmetric Synthesis ◽  
Building Blocks ◽  
Pipecolic Acid ◽  
Aldol Reactions

General Cyclopropane Assembly via Enantioselective Redox-Active Carbene Transfer to Aliphatic Olefins

2018 ◽  
Author(s):  
Marc Montesinos-Magraner ◽  
Matteo Costantini ◽  
Rodrigo Ramirez-Contreras ◽  
Michael E. Muratore ◽  
Magnus J. Johansson ◽  
...  
Keyword(s):  
Total Synthesis ◽  
Asymmetric Synthesis ◽  
Chemical Space ◽  
Synthetic Approach ◽  
Asymmetric Cyclopropanation ◽  
Redox Active ◽  
Wide Range ◽  
Leaving Group ◽  
Stereoelectronic Properties ◽  
Carbene Transfer

Asymmetric cyclopropane synthesis currently requires bespoke strategies, methods, substrates and reagents, even when targeting similar compounds. This limits the speed and chemical space available for discovery campaigns. Here we introduce a practical and versatile diazocompound, and we demonstrate its performance in the first unified asymmetric synthesis of functionalized cyclopropanes. We found that the redox-active leaving group in this reagent enhances the reactivity and selectivity of geminal carbene transfer. This effect enabled the asymmetric cyclopropanation of a wide range of olefins including unactivated aliphatic alkenes, enabling the 3-step total synthesis of (–)-dictyopterene A. This unified synthetic approach delivers high enantioselectivities that are independent of the stereoelectronic properties of the functional groups transferred. Our results demonstrate that orthogonally-differentiated diazocompounds are viable and advantageous equivalents of single-carbon chirons<i>.</i>

Organocatalytic Asymmetric Synthesis of Chiral Pyrrolizines by Cascade Conjugate Addition−Aldol Reactions

2010 ◽  
Vol 12 (19) ◽  
pp. 4352-4355 ◽  
Author(s):  
Ju-Yeon Bae ◽  
Hyo-Jun Lee ◽  
Seok-Ho Youn ◽  
Su-Hyun Kwon ◽  
Chang-Woo Cho
Keyword(s):  
Asymmetric Synthesis ◽  
Conjugate Addition ◽  
Aldol Reactions

scholarly journals Catalytic Asymmetric Synthesis of Acyclic Arrays by Tandem 1,4-Addition-Aldol Reactions

2006 ◽  
Vol 128 (46) ◽  
pp. 14977-14985 ◽  
Author(s):  
Gareth P. Howell ◽  
Stephen P. Fletcher ◽  
Koen Geurts ◽  
Bjorn ter Horst ◽  
Ben L. Feringa
Keyword(s):  
Asymmetric Synthesis ◽  
Aldol Reactions ◽  
Catalytic Asymmetric Synthesis ◽  
Catalytic Asymmetric

Asymmetric Synthesis of Unsaturated Pipecolic Acid Derivatives

Synlett ◽  
1997 ◽  
Vol 1997 (7) ◽  
pp. 799-800 ◽  
Author(s):  
Claude Agami ◽  
Dominique Bihan ◽  
Rémy Morgentin ◽  
Cathy Puchot-Kadouri
Keyword(s):  
Asymmetric Synthesis ◽  
Pipecolic Acid

scholarly journals Heronapyrrole D: A case of co-inspiration of natural product biosynthesis, total synthesis and biodiscovery

2014 ◽  
Vol 10 ◽  
pp. 1228-1232 ◽  
Author(s):  
Jens Schmidt ◽  
Zeinab Khalil ◽  
Robert J Capon ◽  
Christian B W Stark
Keyword(s):  
Antibacterial Activity ◽  
Natural Products ◽  
Total Synthesis ◽  
Asymmetric Synthesis ◽  
Natural Product ◽  
Joint Effort ◽  
Natural Product Biosynthesis ◽  
New Members ◽  
Degree Of Oxidation ◽  
Rare Class

The heronapyrroles A–C have first been isolated from a marine-derived Streptomyces sp. (CMB-0423) in 2010. Structurally, these natural products feature an unusual nitropyrrole system to which a partially oxidized farnesyl chain is attached. The varying degree of oxidation of the sesquiterpenyl subunit in heronapyrroles A–C provoked the hypothesis that there might exist other hitherto unidentified metabolites. On biosynthetic grounds a mono-tetrahydrofuran-diol named heronapyrrole D appeared a possible candidate. We here describe a short asymmetric synthesis of heronapyrrole D, its detection in cultivations of CMB-0423 and finally the evaluation of its antibacterial activity. We thus demonstrate that biosynthetic considerations and the joint effort of synthetic and natural product chemists can result in the identification of new members of a rare class of natural products.

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