Indium-promoted diastereoselective addition of fluorinated haloallylic derivatives to imines.

We report herein the first general access to fluorinated homoallylic amines by means of an addition of fluorinated organoindium reagent. The corresponding amines were obtained in good to excellent yield with excellent diastereoisomeric ratio. A plausible mechanism is proposed to explain the stereochemical outcome of the reaction based on the X-ray structure of the products.

[1]  X. Pannecoucke,et al.  Fluorinated Pseudopeptide Analogues of the Neuropeptide 26RFa: Synthesis, Biological, and Structural Studies , 2013, Chembiochem : a European journal of chemical biology.

[2]  C. Wolf,et al.  Catalytic enantioselective difluoroalkylation of aldehydes. , 2013, Angewandte Chemie.

[3]  X. Pannecoucke,et al.  Copper catalyzed β-difluoroacetylation of dihydropyrans and glycals by means of direct C-H functionalization. , 2013, Organic letters.

[4]  X. Pannecoucke,et al.  A practical and straightforward access to fluorinated homoallylic alcohols in aqueous media , 2013 .

[5]  X. Pannecoucke,et al.  Straightforward asymmetric synthesis of Ala-Ψ[CFCH]-Pro, a proline-containing pseudodipeptide bearing a fluoroolefin as a peptide bond mimic , 2013 .

[6]  X. Pannecoucke,et al.  Palladium- and copper-catalyzed stereocontrolled direct C-H fluoroalkenylation of heteroarenes using gem-bromofluoroalkenes. , 2013, Angewandte Chemie.

[7]  X. Pannecoucke,et al.  Synthesis of fluorinated cyclopropyl amino acid analogues: toward the synthesis of original fluorinated peptidomimetics. , 2013, The Journal of organic chemistry.

[8]  T. Loh,et al.  Organoindium reagents: the preparation and application in organic synthesis. , 2013, Chemical reviews.

[9]  X. Pannecoucke,et al.  Syntheses and applications of monofluorinated cyclopropanes. , 2012, Chemistry.

[10]  Q. Shen,et al.  Preparation of trifluorostyrenes via palladium-catalyzed coupling of arylboronic acids with chloro- and bromotrifluoroethylene. , 2012, The Journal of organic chemistry.

[11]  X. Pannecoucke,et al.  Indium-promoted Reformatsky reaction: a straightforward access to β-amino and β-hydroxy α,α-difluoro carbonyl compounds. , 2012, The Journal of organic chemistry.

[12]  X. Pannecoucke,et al.  Asymmetric synthesis of cyclopropanes with a monofluorinated quaternary stereocenter. , 2012, Organic letters.

[13]  Jinbo Hu,et al.  Reactions of sulfur- and phosphorus-substituted fluoroalkylating silicon reagents with imines and enamines under acidic conditions. , 2012, The Journal of organic chemistry.

[14]  H. Yanai,et al.  Synthetic Methods for Fluorinated Olefins , 2011 .

[15]  B. Singaram,et al.  Nature of the Intermediates Formed During Indium Mediated Allylation under Barbier Conditions. Spectroscopic and Experimental Data on Allylindium Species , 2011 .

[16]  M. Yus,et al.  Catalytic enantioselective allylation of carbonyl compounds and imines. , 2011, Chemical reviews.

[17]  J. Paquin,et al.  Synthetic approaches to monofluoroalkenes. , 2011, Chemical Society reviews.

[18]  Colin Hong An Wong,et al.  Direct synthesis of ester-containing indium homoenolate and its application in palladium-catalyzed cross-coupling with aryl halide. , 2011, Chemical communications.

[19]  J. Fossey,et al.  Catalytic enantioselective formation of C-C bonds by addition to imines and hydrazones: a ten-year update. , 2011, Chemical reviews.

[20]  Colin Hong An Wong,et al.  Palladium-catalyzed cross-coupling of indium homoenolate with aryl halide with wide functional group compatibility. , 2011, Organic letters.

[21]  Colin Hong An Wong,et al.  Direct synthesis of water-tolerant alkyl indium reagents and their application in palladium-catalyzed couplings with aryl halides. , 2011, Angewandte Chemie.

[22]  Colin Hong An Wong,et al.  Synthesis of water-tolerant indium homoenolate in aqueous media and its application in the synthesis of 1,4-dicarbonyl compounds via palladium-catalyzed coupling with acid chloride. , 2010, Journal of the American Chemical Society.

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

[24]  P. Jubault,et al.  First efficient synthesis of fluorinated glycidic esters from ketones. , 2010, Organic letters.

[25]  P. Jubault,et al.  Diethylzinc-mediated one-step stereoselective synthesis of alpha-fluoroacrylates from aldehydes and ketones. Two different pathways depending on the carbonyl partner. , 2009, The Journal of organic chemistry.

[26]  P. Knochel,et al.  LiCl-mediated preparation of functionalized benzylic indium(III) halides and highly chemoselective palladium-catalyzed cross-coupling in a protic cosolvent. , 2009, Angewandte Chemie.

[27]  P. Knochel,et al.  Preparation of aryl and heteroaryl indium(III) reagents by the direct insertion of indium in the presence of LiCl. , 2008, Angewandte Chemie.

[28]  M. Striccoli,et al.  Synthesis of Poly(arylenevinylene)s with Fluorinated Vinylene Units , 2008 .

[29]  S. Purser,et al.  Fluorine in medicinal chemistry. , 2008, Chemical Society reviews.

[30]  David O'Hagan,et al.  Understanding organofluorine chemistry. An introduction to the C-F bond. , 2008, Chemical Society reviews.

[31]  F. Diederich,et al.  Fluorine in Pharmaceuticals: Looking Beyond Intuition , 2007, Science.

[32]  X. Pannecoucke,et al.  Chiral dipeptide mimics possessing a fluoroolefin moiety: a relevant tool for conformational and medicinal studies. , 2007, Organic & biomolecular chemistry.

[33]  Roberta Ragni,et al.  Fluorinated organic materials for electronic and optoelectronic applications: the role of the fluorine atom. , 2007, Chemical communications.

[34]  X. Pannecoucke,et al.  Diastereomeric fluoroolefins as peptide bond mimics prepared by asymmetric reductive amination of alpha-fluoroenones. , 2007, Angewandte Chemie.

[35]  K. Bergander,et al.  Asymmetric Synthesis of ?-Fluorinated a-Amino Acid Derivatives. , 2005 .

[36]  M. Promo,et al.  3-Methyl-4H-[1,2,4]-oxadiazol-5-one: a versatile synthon for protecting monosubstituted acetamidines , 2004 .

[37]  J. Podlech,et al.  Indium in Organic Synthesis , 2003 .

[38]  T. Chan,et al.  Organometallic reactions in aqueous media. Indium- and zinc-mediated allylation of sulfonimines. , 2000, The Journal of organic chemistry.

[39]  E. Wegelius,et al.  Stereoselective Synthesis of γ‐Fluorinated α‐Amino Acids Using 2‐Hydroxy‐3‐pinanone as an Auxiliary , 2000 .

[40]  C. Mück‐Lichtenfeld,et al.  Enantioselective syntheses of 2-amino-4-fluoropent-4-enoic acids. Isosteres of asparagine , 1999 .

[41]  H. Ishitani,et al.  Catalytic enantioselective addition to imines. , 1999, Chemical reviews.

[42]  Yang Yang,et al.  Indium-Mediated Organometallic Reactions in Aqueous Media: The Nature of the Allylindium Intermediate , 1999 .

[43]  L. Paquette,et al.  Comparative Diastereoselectivity Analysis of Crotylindium and 3-Bromoallylindium Additions to alpha-Oxy Aldehydes in Aqueous and Nonaqueous Solvent Systems. , 1996, The Journal of organic chemistry.

[44]  D. Seebach,et al.  Self-Regeneration of Stereocenters (SRS)—Applications, Limitations, and Abandonment of a Synthetic Principle†‡ , 1996 .

[45]  T. Chan,et al.  Indium mediated coupling of aldehydes with allyl bromides in aqueous media. the issue of regio- and diastereo-selectivity , 1995 .

[46]  Karl M. Smith,et al.  Total synthesis of (.+-.)-fawcettimine , 1989 .

[47]  Y. Butsugan,et al.  Indium in organic synthesis: indium-mediated allylation of carbonyl compounds , 1988 .

[48]  E. H. Gold,et al.  Reductive cleavage of sulfonamides with sodium bis(2-methoxyethoxy)aluminum hydride , 1972 .

[49]  S. Hara Stereoselective synthesis of mono-fluoroalkenes. , 2012, Topics in current chemistry.

[50]  Y. Itoh,et al.  Fluorinated carbonyl and olefinic compounds: basic character and asymmetric catalytic reactions. , 2004, Chemical reviews.

[51]  J. Ellman,et al.  Asymmetric Synthesis of α,α-Dibranched Amines by the Trimethylaluminum-Mediated 1,2-Addition of Organolithiums to tert-Butanesulfinyl Ketimines , 1999 .

[52]  D. Seebach,et al.  Resolution and use in α-amino acid synthesis of imidazolidinone glycine derivatives , 1988 .