Enantioselective Synthesis of α-oxy Amides Via Umpolung Amide Synthesis

Overview

Journal J Am Chem Soc

Publisher American Chemical Society

Specialty Chemistry

Date 2012 Sep 13

PMID 22967461

Citations 18

Authors

Matthew W Leighty

Bo Shen

Jeffrey N Johnston

Affiliations

Soon will be listed here.

Abstract

α-Oxy amides are prepared through enantioselective synthesis using a sequence beginning with a Henry addition of bromonitromethane to aldehydes and finishing with Umpolung Amide Synthesis (UmAS). Key to high enantioselection is the finding that ortho-iodo benzoic acid salts of the chiral copper(II) bis(oxazoline) catalyst deliver both diastereomers of the Henry adduct with high enantiomeric excess, homochiral at the oxygen-bearing carbon. Overall, this approach to α-oxy amides provides an innovative complement to alternatives that focus almost entirely on the enantioselective synthesis of α-oxy carboxylic acids.

Citing Articles

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References

Evans D, Seidel D, Rueping M, Lam H, Shaw J, Downey C . A new copper acetate-bis(oxazoline)-catalyzed, enantioselective Henry reaction. J Am Chem Soc. 2003; 125(42):12692-3. DOI: 10.1021/ja0373871. View

Kakei H, Nemoto T, Ohshima T, Shibasaki M . Efficient synthesis of chiral alpha- and beta-hydroxy amides: application to the synthesis of (R)-fluoxetine. Angew Chem Int Ed Engl. 2004; 43(3):317-20. DOI: 10.1002/anie.200352431. View

van Pelt S, Zhang M, Otten L, Holt J, Sorokin D, van Rantwijk F . Probing the enantioselectivity of a diverse group of purified cobalt-centred nitrile hydratases. Org Biomol Chem. 2011; 9(8):3011-9. DOI: 10.1039/c0ob01067g. View

Blay G, Fernandez I, Marco-Aleixandre A, Pedro J . Mandelamide-zinc-catalyzed enantioselective alkyne addition to heteroaromatic aldehydes. J Org Chem. 2006; 71(17):6674-7. DOI: 10.1021/jo0610255. View

Wang S, Wang M, Wang D, Zhu J . Catalytic enantioselective Passerini three-component reaction. Angew Chem Int Ed Engl. 2007; 47(2):388-91. DOI: 10.1002/anie.200704315. View

Arai T, Takashita R, Endo Y, Watanabe M, Yanagisawa A . Asymmetric syn-selective Henry reaction catalyzed by the sulfonyldiamine-CuCl-pyridine system. J Org Chem. 2008; 73(13):4903-6. DOI: 10.1021/jo800412x. View

Blay G, Domingo L, Hernandez-Olmos V, Pedro J . New highly asymmetric Henry reaction catalyzed by Cu(II) and a C(1)-symmetric aminopyridine ligand, and its application to the synthesis of miconazole. Chemistry. 2008; 14(15):4725-30. DOI: 10.1002/chem.200800069. View

Uraguchi D, Nakamura S, Ooi T . Catalytic asymmetric direct Henry reaction of ynals: short syntheses of (2S,3R)-(+)-xestoaminol C and (-)-codonopsinines. Angew Chem Int Ed Engl. 2010; 49(41):7562-5. DOI: 10.1002/anie.201004072. View

Shen B, Makley D, Johnston J . Umpolung reactivity in amide and peptide synthesis. Nature. 2010; 465(7301):1027-32. PMC: 2945247. DOI: 10.1038/nature09125. View

10.

Bandini M, Piccinelli F, Tommasi S, Umani-Ronchi A, Ventrici C . Highly enantioselective nitroaldol reaction catalyzed by new chiral copper complexes. Chem Commun (Camb). 2007; (6):616-8. DOI: 10.1039/b613019d. View

11.

Spry C, Kirk K, Saliba K . Coenzyme A biosynthesis: an antimicrobial drug target. FEMS Microbiol Rev. 2008; 32(1):56-106. DOI: 10.1111/j.1574-6976.2007.00093.x. View

12.

Ube H, Terada M . Enantioselective Henry (nitroaldol) reaction catalyzed by axially chiral guanidines. Bioorg Med Chem Lett. 2009; 19(14):3895-8. DOI: 10.1016/j.bmcl.2009.03.097. View

13.

Denmark S, Fan Y . The first catalytic, asymmetric alpha-additions of isocyanides. Lewis-base-catalyzed, enantioselective Passerini-type reactions. J Am Chem Soc. 2003; 125(26):7825-7. DOI: 10.1021/ja035410c. View

14.

Andreana P, Liu C, Schreiber S . Stereochemical control of the Passerini reaction. Org Lett. 2004; 6(23):4231-3. PMC: 4134661. DOI: 10.1021/ol0482893. View

15.

Yamamoto Y, Shirai T, Miyaura N . Asymmetric addition of arylboronic acids to glyoxylate catalyzed by a ruthenium/Me-BIPAM complex. Chem Commun (Camb). 2012; 48(22):2803-5. DOI: 10.1039/c2cc17339e. View

16.

Christensen C, Juhl K, Jorgensen K . Catalyhtic asymmetric Henry reactions--a simple approach to optically active beta-nitro alpha-hydroxy esters. Chem Commun (Camb). 2002; (21):2222-3. DOI: 10.1039/b105929g. View

17.

Blay G, Hernandez-Olmos V, Pedro J . A catalytic highly enantioselective direct synthesis of 2-bromo-2-nitroalkan-1-ols through a Henry reaction. Chem Commun (Camb). 2008; (39):4840-2. DOI: 10.1039/b809739a. View

18.

Fauq A, Simpson K, Maharvi G, Golde T, Das P . A multigram chemical synthesis of the gamma-secretase inhibitor LY411575 and its diastereoisomers. Bioorg Med Chem Lett. 2007; 17(22):6392-5. PMC: 2962444. DOI: 10.1016/j.bmcl.2007.07.062. View

19.

Du D, Lu S, Fang T, Xu J . Asymmetric Henry reaction catalyzed by C2-symmetric tridentate bis(oxazoline) and bis(thiazoline) complexes: metal-controlled reversal of enantioselectivity. J Org Chem. 2005; 70(9):3712-5. DOI: 10.1021/jo050097d. View

20.

Ding Z, Chen F, Qin J, He Y, Fan Q . Asymmetric hydrogenation of 2,4-disubstituted 1,5-benzodiazepines using cationic ruthenium diamine catalysts: an unusual achiral counteranion induced reversal of enantioselectivity. Angew Chem Int Ed Engl. 2012; 51(23):5706-10. DOI: 10.1002/anie.201200309. View