Base-Controlled Diastereoselective Synthesis of Either anti- or syn-β-Aminonitriles.

Deprotonation of secondary alkane nitriles with nBuLi and addition to aryl imines gives kinetic anti-β-aminonitriles. Use of LHMDS allows reversible protonation of the reaction intermediate to give syn-β-aminonitriles. The pure diastereosiomers can be isolated in good yields, and the mechanism was elucidated.

[1]  Hanmin Huang,et al.  Synthetic methods for 1,3-diamines. , 2016, Organic & biomolecular chemistry.

[2]  Ming Yan,et al.  11-Step Total Synthesis of Araiosamines , 2016, Journal of the American Chemical Society.

[3]  G. Tizzard,et al.  Reductive conjugate addition nitro-Mannich route for the stereoselective synthesis of 1,2,3,4-tetrahydroquinoxalines. , 2016, Organic & biomolecular chemistry.

[4]  C. Palomo,et al.  Cyanoalkylation: Alkylnitriles in Catalytic C-C Bond-Forming Reactions. , 2015, Angewandte Chemie.

[5]  James C. Anderson,et al.  Stereoselective Synthesis of Densely Substituted Tetrahydroquinolines by a Conjugate Addition Nitro-Mannich Reaction with Carbon Nucleophiles , 2015, Synlett.

[6]  James C. Anderson,et al.  Asymmetric Intramolecular Conjugate Addition Nitro-Mannich Route to cis-2-Aryl-3-nitrotetrahydroquinolines. , 2015, Organic letters.

[7]  D. Tocher,et al.  Stereoselective synthesis of 1,2-diamine containing indolines by a conjugate addition nitro-Mannich reaction. , 2015, Organic & biomolecular chemistry.

[8]  A. Kalogirou,et al.  Conjugate addition nitro-Mannich reaction of carbon and heteroatom nucleophiles to nitroalkenes , 2014 .

[9]  A. Kalogirou,et al.  Synthesis of the reported structure of piperazirum using a nitro-Mannich reaction as the key stereochemical determining step , 2013, Beilstein journal of organic chemistry.

[10]  James C. Anderson,et al.  An enantioselective tandem reduction/nitro-Mannich reaction of nitroalkenes using a simple thiourea organocatalyst , 2013 .

[11]  Y. Funahashi,et al.  Catalytic enantioselective decarboxylative cyanoalkylation of imines by using palladium pincer complexes with C2-symmetric chiral bis(imidazoline)s. , 2013, Chemistry.

[12]  Lili Lin,et al.  Asymmetric synthesis of β-amino nitriles through a Sc(III)-catalyzed three-component Mannich reaction of silyl ketene imines. , 2013, Angewandte Chemie.

[13]  D. Tocher,et al.  Reductive nitro-Mannich route for the synthesis of 1,2-diamine containing indolines and tetrahydroquinolines. , 2012, The Journal of organic chemistry.

[14]  A. Kalogirou,et al.  Stereoselective synthesis of densely functionalized pyrrolidin-2-ones by a conjugate addition/nitro-Mannich/lactamization reaction. , 2012, The Journal of organic chemistry.

[15]  A. J. Blake,et al.  Diastereoselective reductive nitro-Mannich reactions. , 2012, The Journal of organic chemistry.

[16]  D. Brady,et al.  Enantioselective biocatalytic hydrolysis of β-aminonitriles to β-amino-amides using Rhodococcus rhodochrous ATCC BAA-870 , 2012 .

[17]  Y. Funahashi,et al.  Enantioselective Reaction of Imines and Benzyl Nitriles Using Palladium Pincer Complexes with C2‐Symmetric Chiral Bis(imidazoline)s , 2011 .

[18]  F. Fleming,et al.  Nitrile-containing pharmaceuticals: efficacious roles of the nitrile pharmacophore. , 2010, Journal of medicinal chemistry.

[19]  J. Ellman,et al.  Synthesis and applications of tert-butanesulfinamide. , 2010, Chemical reviews.

[20]  T. Poisson,et al.  Product-catalyzed addition of alkyl nitriles to unactivated imines promoted by sodium aryloxide/ethyl(trimethylsilyl)acetate (ETSA) combination. , 2009, The Journal of organic chemistry.

[21]  Juhanes Aydin,et al.  Stereoselective Pincer-complex catalyzed C-H functionalization of benzyl nitriles under mild conditions. An efficient route to beta-aminonitriles. , 2008, Organic letters.

[22]  A. J. Blake,et al.  A general one-step synthesis of beta-nitronitriles. , 2008, Organic letters.

[23]  S. Simova,et al.  Diastereoselectivity in addition of nitrile-stabilized carbanions to Schiff bases and in subsequent alkylation reactions , 2005 .

[24]  J. Yadav,et al.  Lithium perchlorate catalyzed regioselective ring opening of aziridines with sodium azide and sodium cyanide , 2002 .

[25]  M. Petrini,et al.  Reaction of α-Amidoalkylphenyl Sulfones with Lithiated Nitriles: Syn-Selective Synthesis of β-Amino Nitriles , 2001 .

[26]  J. Verkade,et al.  P(RNCH(2)CH(2))(3)N-Catalyzed Synthesis of beta-Hydroxy Nitriles. , 1999, The Journal of organic chemistry.

[27]  Jiali Gao,et al.  Experimental and Computational Determination of the Effect of the Cyano Group on Carbon Acidity in Water , 1999 .

[28]  J. Verkade,et al.  Direct Synthesis of α,β-Unsaturated Nitriles Catalyzed by Nonionic Superbases , 1998 .

[29]  T. Oki,et al.  Beta-cyanoglutamic acid, a new antifungal amino acid from a streptomycete. , 1993, The Journal of antibiotics.

[30]  F. G. Bordwell,et al.  Equilibrium Acidities in Dimethyl Sulfoxide Solution , 1988 .

[31]  R. Verpoorte,et al.  Some new vallesamine-type alkaloids , 1987 .

[32]  D. Watt,et al.  Addition and Substitution Reactions of Nitrile-Stabilized Carbanions , 1984 .

[33]  D. Garvey,et al.  Highly Stereoselective Aldol Condensation Using an Enantioselective Chiral Enolate , 1980 .

[34]  F. Fleming.  Nitrile-containing natural products , 1999 .

[35]  Z. Rappoport.  The Cyano Group (1970) , 1970 .