Rhodium-catalyzed Carbonylative Annulation of 2-Bromobenzylic Alcohols with Internal Alkynes Using Furfural via β-Aryl Elimination

In spite of the significant progress made in transformations of unstrained benzylic (tert-)alcohols through β-aryl elimination, catalytic carbonylation has not yet been developed extensively because alkoxycarbonylation is probably favored over β-aryl elimination. In this letter, we report on the rhodium(I)-catalyzed carbonylative annulation of α,α-dimethyl-(2-bromoaryl)methanols with internal alkynes using furfural leading to the formation of indenones. The key to the success of the reaction is the timely generation of the carbonyl source via the decarbonylation of furfural.

[1]  Zheng Xu,et al.  Transition-metal-catalyzed transfer carbonylation with HCOOH or HCHO as non-gaseous C1 source , 2017 .

[2]  K. Kakiuchi,et al.  Rhodium(I)‐Catalyzed Carbonylative Annulation of Iodobenzenes with Strained Olefins and 4‐Octyne in the Presence of Furfural Involving ortho‐C–H Bond Cleavage , 2017 .

[3]  G. Fumagalli,et al.  Recent Methodologies That Exploit C-C Single-Bond Cleavage of Strained Ring Systems by Transition Metal Complexes. , 2017, Chemical reviews.

[4]  Xiao‐Feng Wu,et al.  Recent Achievements in Carbonylation Reactions: A Personal Account , 2016, Synlett.

[5]  M. Murakami,et al.  Potential of Metal-Catalyzed C-C Single Bond Cleavage for Organic Synthesis. , 2016, Journal of the American Chemical Society.

[6]  J. Mascareñas,et al.  Metal-Catalyzed Annulations through Activation and Cleavage of C-H Bonds. , 2016, Angewandte Chemie.

[7]  G. Satyanarayana,et al.  Domino [Pd]-Catalysis: One-Pot Synthesis of Isobenzofuran-1(3H)-ones. , 2016, The Journal of organic chemistry.

[8]  K. Kakiuchi,et al.  Rh(I) -Catalyzed Intramolecular Carbonylative C-H/C-I Coupling of 2-Iodobiphenyls Using Furfural as a Carbonyl Source. , 2016, Chemistry, an Asian journal.

[9]  B. Bhanage,et al.  Transition Metal-Catalyzed Carbonylative C-H Bond Functionalization of Arenes and C(sp(3))-H Bond of Alkanes. , 2016, Chemical record.

[10]  T. Skrydstrup,et al.  The Development and Application of Two-Chamber Reactors and Carbon Monoxide Precursors for Safe Carbonylation Reactions. , 2016, Accounts of chemical research.

[11]  T. Kondo.  Ruthenium‐ and Rhodium‐Catalyzed Strain‐Driven Cleavage and Reconstruction of the C–C Bond , 2016 .

[12]  Xiao‐Feng Wu,et al.  Palladium-catalyzed carbonylative C–H activation of arenes with norbornene as the coupling partner , 2016 .

[13]  K. Kakiuchi,et al.  Pd(0)-Catalyzed CO Gas-Free Carbonylation of 2-Bromobiphenyls with Formaldehyde as a Carbonyl Surrogate through the Cleavage of a C-H Bond , 2016 .

[14]  M. Murakami.  Cleavage of Carbon-Carbon Single Bonds by Transition Metals: Murakami/Cleavage of Carbon-Carbon Single Bonds by Transition Metals , 2015 .

[15]  Xiao‐Feng Wu,et al.  The Applications of (Para)formaldehyde in Metal‐Catalyzed Organic Synthesis , 2015 .

[16]  M. Gao,et al.  Oxidative Coupling between Two Hydrocarbons: An Update of Recent C-H Functionalizations. , 2015, Chemical reviews.

[17]  P. R. Rajamohanan,et al.  Reversed reactivity of anilines with alkynes in the rhodium-catalysed C–H activation/carbonylation tandem , 2015, Nature Communications.

[18]  B. Bhanage,et al.  Recent advances in the transition metal catalyzed carbonylation of alkynes, arenes and aryl halides using CO surrogates , 2015 .

[19]  Y. Nishihara,et al.  Synthesis of Multisubstituted Triphenylenes and Phenanthrenes by Cascade Reaction of o-Iodobiphenyls or (Z)-β-Halostyrenes with o-Bromobenzyl Alcohols through Two Sequential C-C Bond Formations Catalyzed by a Palladium Complex. , 2015, The Journal of organic chemistry.

[20]  N. Cramer,et al.  Catalytic C-C Bond Activations via Oxidative Addition to Transition Metals. , 2015, Chemical reviews.

[21]  R. Franke,et al.  Regioselective Pd-catalyzed methoxycarbonylation of alkenes using both paraformaldehyde and methanol as CO surrogates. , 2015, Angewandte Chemie.

[22]  Lei Yang,et al.  Transition-metal-catalyzed direct addition of unactivated C-H bonds to polar unsaturated bonds. , 2015, Chemical reviews.

[23]  K. Kakiuchi,et al.  Asymmetric Pauson–Khand-type reactions of 1,6-enynes using formaldehyde as a carbonyl source by cooperative dual rhodium catalysis , 2015 .

[24]  I. Marek,et al.  Selective carbon-carbon bond cleavage for the stereoselective synthesis of acyclic systems. , 2015, Angewandte Chemie.

[25]  Hu Li,et al.  Catalysis in C–C Activation , 2014 .

[26]  Zhangjie Shi,et al.  Homogeneous Transition‐Metal‐Catalyzed C–H Bond Functionalization , 2014 .

[27]  M. Beller,et al.  Ruthenium‐Catalyzed Alkoxycarbonylation of Alkenes with Paraformaldehyde as a Carbon Monoxide Substitute , 2014 .

[28]  N. Jiao,et al.  Recent advances in transition-metal-catalyzed functionalization of unstrained carbon-carbon bonds. , 2014, Chemical reviews.

[29]  K. Manabe,et al.  Formic Acid Derivatives as Practical Carbon Monoxide Surrogates for Metal-Catalyzed Carbonylation Reactions , 2014 .

[30]  M. Beller,et al.  Carbonylations of alkenes with CO surrogates. , 2014, Angewandte Chemie.

[31]  L. Lo,et al.  Palladium-catalyzed annulation of internal alkynes in aqueous medium , 2014 .

[32]  Guangbin Dong,et al.  C-C Bond Activation , 2014 .

[33]  Y. Nishihara,et al.  Palladium-catalyzed annulation of o-iodobiphenyls with o-bromobenzyl alcohols: synthesis of functionalized triphenylenes via C-C and C-H bond cleavages. , 2013, Organic letters.

[34]  M. Beller,et al.  Carbonylative C–H Activations , 2013 .

[35]  K. Kakiuchi,et al.  Rh(I)-catalyzed asymmetric synthesis of 3-substituted isoindolinones through CO gas-free aminocarbonylation. , 2012, The Journal of organic chemistry.

[36]  M. Larhed,et al.  Molybdenum Hexacarbonyl MediatedCO Gas-Free Carbonylative Reactions , 2012 .

[37]  G. Satyanarayana,et al.  A domino palladium-catalyzed C-C and C-O bonds formation via dual O-H bond activation: synthesis of 6,6-dialkyl-6H-benzo[c]chromenes. , 2012, Organic letters.

[38]  K. Hirano,et al.  Synthesis of isochromene and related derivatives by rhodium-catalyzed oxidative coupling of benzyl and allyl alcohols with alkynes. , 2011, The Journal of organic chemistry.

[39]  Zhangjie Shi,et al.  Introduction: CH Activation. , 2017, Chemical reviews.

[40]  Zhenyang Lin,et al.  Theoretical studies on beta-aryl elimination from Rh(I) complexes. , 2009, Dalton transactions.

[41]  Toshihiko Uto,et al.  Rhodium-catalyzed oxidative coupling of triarylmethanols with internal alkynes via successive C-H and C-C bond cleavages. , 2008, The Journal of organic chemistry.

[42]  M. Murakami,et al.  Rhodium-catalyzed carbonylation of spiropentanes. , 2007, Journal of the American Chemical Society.

[43]  Tamio Hayashi,et al.  Rhodium‐Catalyzed Aryl Transfer from Trisubstituted Aryl Methanols to α,β‐Unsaturated Carbonyl Compounds , 2007 .

[44]  N. Chatani,et al.  Rh(I)-catalyzed carbonylative cyclization reactions of alkynes with 2-bromophenylboronic acids leading to indenones. , 2007, Journal of the American Chemical Society.

[45]  R. Larock,et al.  Applications of the palladium-catalyzed carbonylative annulation of internal alkynes to the synthesis of medium-sized rings , 2007 .

[46]  A. Kotschy,et al.  Selective Palladium-Catalysed ipso Arylation of α,α-Disubstituted Benzo[b]thien-2-ylmethanols with Aryl Bromides using PCy3 as Ligand , 2007 .

[47]  T. Satoh,et al.  Palladium-catalyzed selective 2,3-diarylation of α,α-disubstituted 3-thiophenemethanols via cleavage of C-H and C-C bonds , 2006 .

[48]  C. Incarvito,et al.  Direct Observation of β-Aryl Eliminations from Rh(I) Alkoxides , 2006 .

[49]  K. Kakiuchi,et al.  Evolution of carbonylation catalysis: no need for carbon monoxide. , 2004, Angewandte Chemie.

[50]  T. Satoh,et al.  Palladium-catalyzed dehydroarylation of triarylmethanols and their coupling with unsaturated compounds accompanied by C-C bond cleavage. , 2004, The Journal of organic chemistry.

[51]  R. Larock,et al.  Palladium-catalyzed carbonylative annulation of internal alkynes: synthesis of 3,4-disubstituted coumarins. , 2003, The Journal of organic chemistry.

[52]  T. Satoh,et al.  Palladium-Catalyzed Arylation of α,α-Disubstituted Arylmethanols via Cleavage of a C−C or a C−H Bond To Give Biaryls , 2003 .

[53]  S. Murai,et al.  Catalytic carbonylation reactions of benzyne derivatives. , 2001, Journal of the American Chemical Society.

[54]  T. Satoh,et al.  Palladium-Catalyzed Arylative Carbon−Carbon Bond Cleavage of α,α-Disubstituted Arylmethanols , 2001 .

[55]  R. Perry,et al.  Palladium-Catalyzed Carbonylation and Coupling Reactions of Aryl Chlorides and Amines. , 1996, The Journal of organic chemistry.

[56]  J. Brunet,et al.  Sunlamp-irradiated phase-transfer catalysis. 1. Cobalt carbonyl catalyzed SRN1 carbonylations of aryl and vinyl halides , 1983 .

[57]  J. Stille,et al.  Synthesis of lactones by the palladium-catalyzed carbonylation of halo alcohols , 1980 .