Publication Cover
Synthetic Communications
An International Journal for Rapid Communication of Synthetic Organic Chemistry
Volume 41, 2011 - Issue 8
356
Views
4
CrossRef citations to date
0
Altmetric
Original Articles

Rh-Catalyzed One-Pot Reductive Alkylation of Malononitrile Under Transfer Hydrogenation Conditions

&
Pages 1218-1226 | Received 09 Jul 2009, Published online: 21 Mar 2011

REFERENCES

  • (a) Bower , J. F. ; Kim , I. S. ; Patman , R. L. ; Krische , M. J. Catalytic carbonyl addition through transfer hydrogenation: A departure from preformed organometallic reagents . Angew. Chem. Int. Ed. 2009 , 48 , 34 ; (b) Li , C.-J. Organic reactions in aqueous media with a focus on carbon–carbon bond formations: A decade update . Chem. Rev. 2005 , 105 , 3095 ; (c) Fagnou , K. ; Lautens , M. Rhodium-catalyzed carbon–carbon bond-forming reactions of organometallic compounds . Chem. Rev. 2003 , 103 , 169 ; (d) Culkin , D. A. ; Hartwig , J. F. Palladium-catalyzed α-arylation of carbonyl compounds and nitriles . Acc. Chem. Res. 2003 , 36 , 234 ; (e) Mayr , H. ; Kempf , B. ; Ofial , A. R. π-Nucleophilicity in carbon–carbon bond-forming reactions . Acc Chem. Res. 2003 , 36 , 66 ; (f) Sammelson , R. E. ; Kurth , M. J. Carbon–carbon bond-forming solid-phase reactions, part II . Chem. Rev. 2001 , 101 , 137 .
  • (a) Grossman , R. B. ; Varner , M. A. Selective monoalkylation of diethyl malonate, ethyl cyanoacetate, and malononitrile using a masking group for the second acidic hydrogen . J. Org. Chem. 1997 , 62 , 5235 ; (b) Díez-Barra , E. ; Hoz , A. ; Moreno , A. ; Sánchez-Verdú , P. Phase-transfer catalysis without solvent: Selective mono- or di-alkylation of malononitrile . J. Chem. Soc., Perkin Trans. 1 1991 , 2589 ; (c) Bloomfield , J. Alkylation reactions in dimethyl sulfoxide . J. Org. Chem. 1961 , 26 , 4112 .
  • (a) Tu , Z. ; Lin , C. ; Jand , Y. ; Ko , S. ; Fang , H. ; Liu , J.-T. ; Yao , C.-F. One-pot synthesis of malononitriles by free radical reactions of ylidenemalononitrile with Et3B and iodoalkene in water–ether biphase medium. Tetrahedron Lett. 2006, 47, 6133; (b) Chandrasekhar , S. ; Chandrashekar , G. ; Reddy , M. S. ; Srihari , P. A facile and chemoselective conjugate reduction using polymethylhydrosiloxane (PMHS) and catalytic B (C8F5)3 . Org. Biomol. Chem. 2006, 4, 1650; (c) Adair , G. R. A. ; Kapoor , K. K. ; Scolan , A. L. B. ; Williams , J. M. J. Ruthenium-catalysed reduction of alkenes using sodium borohydride. Tetrahedron Lett. 2006, 47, 8943 (d) Ren , Y. ; Xu , X. ; Sun , K. ; Xu , J. A new and effective method for providing optically active monosubstituted malononitriles: Selective reduction of α,β-unsaturated dinitriles catalyzed by copper hydride complexes. Tetrahedron: Asymmetry. 2005, 16, 4010; (e) Liu , W. ; Cui , X. ; Cun , L. ; Zhu , J. ; Deng , J. Tunable dendritic ligands of chiral 1,2-diamine and their application in asymmetric transfer hydrogenation. Tetrahedron: Asymmetry 2005, 16, 2525; (f) Xue , D. ; Chen , Y.-C. ; Cui , X. ; Wang , Q.-W. ; Zhu , J. ; Deng , J.-G. Transfer hydrogenation of activated C˭C bonds catalyzed by ruthenium amido complexes: Reaction scope, limitation, and enantioselectivity. J. Org. Chem. 2005, 70, 3584 (g) Chen , Y.-C. ; Xue , D. ; Deng , J.-G. ; Cui , X. ; Zhu , J. ; Jiang , Y.-Z. Efficient asymmetric transfer hydrogenation of activated olefins catalyzed by ruthenium amido complexes. Tetrahedron Lett. 2004, 45, 1555; (h) Ranu , B. C. ; Samanta , S. Reduction of activated conjugated alkenes by the InCl3-NaBH4 reagent system. Tetrahedron 2003, 59, 7901; (i) Ranu , B. C. ; Samanta , S. Use of indium hydride (Cl2InH) for chemoselective reduction of the carbon–carbon double bond in conjugated alkenes. Tetrahedron Lett. 2002, 43, 7405; (j) Ranu , B. C. ; Dutta , J. ; Guchhait , S. K. Indium metal as a reducing agent: Selective reduction of the carbon–carbon double bond in highly activated conjugated alkenes. Org. Lett. 2001, 3, 2603; (j) Nanjo , K. ; Suzuki , K. ; Sekiya , M. Formic acid reduction, XXVI: α,β-Reduction of conjugated nitriles with formic acid. Chem. Pharm. Bull. 1977, 25, 2396.
  • (a) Hosseini-Sarvari , M. ; Sharghi , H. ; Etemad , S. Nancocrystalline ZnO for Knoevenagel condensation and reduction of the carbon–carbon double bond in conjugated alkenes . Helv. Chim. Acta. 2008 , 91 , 715 ; (b) Tayyari , F. ; Wood , D. E. ; Fanwick , P. E. ; Sammelson , R. E. Monosubstituted malononitriles: Efficient one-pot reductive alkylations of malononitrile with aromatic aldehydes . Synthesis. 2008 , 279 ; (c) Motokura , K. ; Fujita , N. ; Mori , K. ; Mizugaki , T. ; Ebitani , K. ; Jitsukawa , K. ; Kaneda , K. Environmentally friendly one-pot synthesis of α -alkylated nitriles using hydrotalcite-supported metal species as multifunctional solid catalysts . Chem. Eur. J. 2006 , 12 , 8228 ; (d) Phan , N. T. S. ; Gill , C. S. ; Nguyen , J. V. ; Zhang Z. J. ; Jones , C. W. Expanding the utility of one-pot multistep reaction networks through compartmentation and recovery of the catalyst . Angew. Chem. Int. Ed. 2006 , 45 , 2209 ; (e) Motokura , K. ; Fujita , N. ; Mori , K. ; Mizugaki , T. ; Ebitani , K. ; Kaneda , K. One-pot synthesis of α-alkylated nitriles with carbonyl compounds through consecutive aldol reaction/hydrogenation using a hydrotalcite-supported palladium nanoparticle as a multifunctional heterogeneous catalyst . Tetrahedron Lett. 2005 , 46 , 5507 ; (f) Sammelson , R. E. ; Allen , M. J. A convenient and selective one-pot method for the synthesis of monosubstituted secondary alkyl malononitriles . Synthesis. 2005 , 543 ; (g) Ricketts , B. ; Miller , R. L. ; Sammelson , R. E. Synthesis of mono- and disubstituted malononitrile derivatives: Carbon alkylation selectivity. Abstracts of Papers, 237th ACS National Meeting; Salt Lake City, UT, March 22–29, 2009, CHED-904; American Chemical Society: Washington, DC, 2009 ; (h) Miller , R. L. ; Sammelson , R. E. Selective synthesis of monosubstituted and disubstituted malononitrile derivatives. Abstracts of Papers, 235th ACS National Meeting; New Orleans, LA, April 6–10, 2008, CHED-441; American Chemical Society: Washington, DC, 2008.
  • (a) Ramachary , D. B. ; Kishor , M. ; Reddy , Y. V. Development of pharmaceutical drugs, drug intermediates, and ingredients by using direct organo-click reactions. Eur. J. Org. Chem. 2008, 975; (b) Ramachary , D. B. ; Kishor , M. ; Reddy , G. B. Development of drug intermediates by using direct organocatalytic multicomponent reactions. Org. Biomol. Chem. 2006, 4, 1641; (c) Ramachary , D. B. ; Kishor , M. ; Ramakumar , K. A novel and green protocol for two-carbon homologation: A direct amino acid/K2CO3-catalyzed four-component reaction of aldehyde, active methylenes, Hantzsch esters, and alkyl halides. Tetrahedron Lett. 2006, 47, 651; (d) Zhang , Z. ; Gao , J. ; Xia , J.-J. ; Wang , G.-W. Solvent-free mechanochemical and one-pot reductive benzylizations of malononitrile and 4-methylaniline using Hantzsch 1,4-dihydropyridine as the reductant. Org. Biomol. Chem. 2005, 3, 1617; (e) Ramachary , D. B. ; Reddy , G. B. Toward organo-click reactions: Development of pharmaceutical ingredients by using direct organocatalytic bio-mimetic reductions. Org. Biomol. Chem. 2006, 4, 4463; (f) Kumar , S. ; Kapoor , K. K. Unprecedented reaction between ethyl α-cyanocinnamate and o-phenylenediamine: Development of an efficient method for the transfer hydrogenation of electronically depleted olefins. Synlett. 2007, 2809.
  • Dunham , J. C. ; Richardson , A. D. ; Sammelson , R. E. Sodium borohydride as the only reagent for the efficient reductive alkylation of malononitrile with ketones and aldehydes . Synthesis. 2006 , 680 .
  • (a) Zhang , B. ; Zhu , X.-Q. ; Lu , J.-Y. ; He , J. ; Wang , P. G. ; Cheng , J.-P. Polysiloxane-supported NAD(P)H model 1-benzyl-1,4-dihydronicotinamide: Synthesis and application in the reduction of activated olefins . J. Org. Chem. 2003 , 68 , 3295 ; (b) Westfahl , J. C. ; Gresham , T. L. Vinylidene cyanide, V: The aluminum chloride–catalyzed reaction of vinylidene cyanide and aromatic compounds . J. Am. Chem. Soc. 1953 , 76 , 1076 .

Reprints and Corporate Permissions

Please note: Selecting permissions does not provide access to the full text of the article, please see our help page How do I view content?

To request a reprint or corporate permissions for this article, please click on the relevant link below:

Academic Permissions

Please note: Selecting permissions does not provide access to the full text of the article, please see our help page How do I view content?

Obtain permissions instantly via Rightslink by clicking on the button below:

If you are unable to obtain permissions via Rightslink, please complete and submit this Permissions form. For more information, please visit our Permissions help page.