Transition metal-free hydrodefluorination of acid fluorides and organofluorines by Ph3GeH promoted by catalytic [Ph3C][B(C6F5)4].

It has been shown that the germane Ph3GeH converts aryl and aliphatic acid fluorides directly to their corresponding aldehydes without over-reduction via the conversion of Ph3GeH to the germylium cation [Ph3Ge]+ by a catalytic amount of the tritylium salt [Ph3C][B(C6F5)4]. Here, no transition metal catalyst is required and there is no decarbonylation of the acid fluoride, which are advantages over existing methods. The fluorine atoms can also be abstracted from organofluorine compounds using this method.

[1]  M. Kaupp,et al.  Characterization of hydrogen-substituted silylium ions in the condensed phase , 2019, Science.

[2]  N. Blanchard,et al.  Acid Fluorides in Transition-Metal Catalysis: A Good Balance between Stability and Reactivity. , 2019, Angewandte Chemie.

[3]  Quansheng Wu,et al.  Non-Abelian band topology in noninteracting metals , 2018, Science.

[4]  Yohei Ogiwara,et al.  Palladium-Catalyzed Reductive Conversion of Acyl Fluorides via Ligand-Controlled Decarbonylation. , 2018, Organic letters.

[5]  A. Rheingold,et al.  Synthesis of the Elusive Branched Fluoro-oligogermane (Ph3Ge)3GeF: A Structural, Spectroscopic, Electrochemical, and Computational Study , 2018, Organometallics.

[6]  T. Scattolin,et al.  Direct Synthesis of Acyl Fluorides from Carboxylic Acids with the Bench-Stable Solid Reagent (Me4N)SCF3. , 2017, Organic letters.

[7]  P. J. Brothers,et al.  Synthesis, Electronic Structure, and Reactivity Studies of a 4-Coordinate Square Planar Germanium(IV) Cation. , 2016, Journal of the American Chemical Society.

[8]  T. Stahl,et al.  Main-Group Lewis Acids for C–F Bond Activation , 2013 .

[9]  D. Gutsulyak,et al.  Chemoselective Ruthenium‐Catalyzed Reduction of Acid Chlorides to Aldehydes with Dimethylphenylsilane , 2012 .

[10]  D. Stephan,et al.  Activation of Alkyl C–F Bonds by B(C6F5)3: Stoichiometric and Catalytic Transformations , 2012 .

[11]  M. Brook,et al.  Siloxane-triarylamine hybrids: discrete room temperature liquid triarylamines via the Piers-Rubinsztajn reaction. , 2011, Organic letters.

[12]  M. Brook,et al.  Rapid assembly of explicit, functional silicones. , 2010, Dalton transactions.

[13]  M. Brook,et al.  Testing the functional tolerance of the Piers-Rubinsztajn reaction: a new strategy for functional silicones. , 2010, Chemical communications.

[14]  C. Nagaraja,et al.  Hydrodefluorination and other hydrodehalogenation of aliphatic carbon-halogen bonds using silylium catalysis. , 2010, Journal of the American Chemical Society.

[15]  M. Brook,et al.  New Synthetic Strategies for Structured Silicones Using B(C6F5)3 , 2010 .

[16]  O. Ozerov,et al.  Hydrodefluorination of Perfluoroalkyl Groups Using Silylium-Carborane Catalysts , 2008, Science.

[17]  M. Brook,et al.  Rapid assembly of complex 3D siloxane architectures. , 2008, Journal of the American Chemical Society.

[18]  R. Maleczka,et al.  Pd(0)-Catalyzed PMHS reductions of aromatic acid chlorides to aldehydes. , 2006, Organic letters.

[19]  W. Fortuniak,et al.  Mechanism of the B(C6F5)3-Catalyzed Reaction of Silyl Hydrides with Alkoxysilanes. Kinetic and Spectroscopic Studies , 2005 .

[20]  Chinpiao Chen,et al.  ChemInform Abstract: Preparation of Acyl Fluorides with Hydrogen Fluoride-Pyridine and 1,3-Dicyclohexylcarbodiimide. , 2002 .

[21]  Gevorgyan,et al.  A novel B(C(6)F(5))(3)-catalyzed reduction of alcohols and cleavage of aryl and alkyl ethers with hydrosilanes , 2000, The Journal of organic chemistry.

[22]  Piers,et al.  Studies on the mechanism of B(C(6)F(5))(3)-catalyzed hydrosilation of carbonyl functions , 2000, The Journal of organic chemistry.

[23]  M. Yasuda,et al.  Selective reduction of acid chloride with a catalytic amount of an indium compound , 2000 .

[24]  D. Parks,et al.  SYNTHESIS AND SOLUTION AND SOLID-STATE STRUCTURES OF TRIS(PENTAFLUOROPHENYL)BORANE ADDUCTS OF PHC(O)X (X = H, ME, OET, NPRI2) , 1998 .

[25]  C. Malanga,et al.  Nickel Mediated Conversion of Acyl Halides in Aldehydes , 1997 .

[26]  W. Piers,et al.  Tris(pentafluorophenyl)boron-Catalyzed Hydrosilation of Aromatic Aldehydes, Ketones, and Esters , 1996 .

[27]  J. Vaquero,et al.  Synthesis of aldehydes from acyl chlorides via 1-(acylmethylamino)-3-methylimidazolium salts , 1995 .

[28]  H. Brown,et al.  Exceptionally facile reduction of acid chlorides to aldehydes by sodium tri-tert-butoxyaluminohydride , 1993 .

[29]  T. Himmler,et al.  Katalytische Reduktion von aromatischen Carbonsäurefluoriden zu Aldehyden , 1989 .

[30]  H. Alper,et al.  Selective transfer hydrogenation of various unsaturated functions by polymethylhydrosiloxane in the presence of a recyclable rhodium catalyst , 1986 .

[31]  C. Moïse,et al.  The reaction of Cp2M(CO)H (M = Nb or Ta) complexes with acyl chlorides, a new way to transform acyl chlorides into aldehydes , 1985 .

[32]  P. L. Gaus,et al.  Anionic group 6 transition-metal carbonyl hydrides as reducing agents. ketones, aldehydes, and epoxides , 1985 .

[33]  T. N. Sorrell,et al.  Correction. Preparation of Aldehydes from Acid Chlorides Using Copper Tetrahydroborate Complexes , 1980 .

[34]  H. Brown,et al.  Forty years of hydride reductions , 1979 .

[35]  C. Eaborn,et al.  Interaction of acyl chlorides and triethylsilane catalysed by rhodium complexes , 1975 .

[36]  C. Eaborn,et al.  Interaction of acyl chlorides and triethylsilane catalysed by cis-di-chlorobis(triphenylphosphine)platinum(II) and related complexes , 1975 .

[37]  C. Eaborn,et al.  The interaction of acyl halides and organosilicon hydrides catalysed by platinum and rhodium complexes. A new route to ketones , 1970 .

[38]  J. D. Citron Reductions with organosilicon hydrides. II. Preparation of aldehydes from acyl chlorides , 1969 .

[39]  H. Brown,et al.  LITHIUM TRI-t-BUTOXYALUMINOHYDRIDE-A NEW REAGENT FOR CONVERTING ACID CHLORIDES TO ALDEHYDES , 1956 .