キノリノラトロジウム触媒を用いたアルキン類のアミンとの新規カップリング反応の開発に関する研究 (本文)

序論

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(7) Metal-catalyzed Markovnikov addition of primary and secondary amines to terminal alkynes, see:

(a) Barluenga, J.; Aznar, F.; Liz, R.; Rodes, R. Catalytic and Non-catalytic Addition of Aromatic Amines to Terminal Acetylenes in the Presence of Mercury(II) Chloride and Acetate. J. Chem. Soc., Perkin Trans. I 1980, 2732-2737. (b) Uchimaru, Y. N–H activation vs. C–H activation:ruthenium-catalysed regioselective hydroamination of alkynes and hydroarylation of an alkene with N-methylaniline. Chem. Commun. 1999, 1133-1134. (c) Hartung, C. G.; Tillack, A.; Trauthwein, H.; Beller, M. A Convenient Rhodium-Catalyzed Intermolecular Hydroamination Procedure for Terminal Alkynes. J. Org. Chem. 2001, 66, 6339-6343. (d) Zeng, X.; Frey, G. D.; Kousar, S.; Bertrand, G. A Cationic Gold(I) Complex as a General Catalyst for the Intermolecular Hydroamination of Alkynes: Application to the One-Pot Synthesis of Allenes from Two Alkynes and a Sacrificial Amine. Chem. Eur. J. 2009, 15, 3056-3060.

(8) Base-catalyzed anti-Markovnikov hydroamination of terminal alkynes with secondary amines, see: (a) Tzalis, D.; Koradin, C.; Knochel, P. Cesium hydroxide catalyzed addition of alcohols and amine derivatives to alkynes and styrene. Tetrahedron Lett. 1999, 40, 6193-6195. (b) Zhao, N.; Lin, C.; Wen, L.; Li, Z. Anti-Markovnikov stereoselective hydroamination and hydrothiolation of (hetero)aromatic alkynes using a metal-free cyclic trimeric phosphazene base. Tetrahedron 2019, 75, 3432-3440. (c) Verma, A. K.; Patel, M.; Joshi, M.; Likhar, P. R.; Tiwari, R. K.; Parang, K. Base-Mediated Chemo- and Stereoselective Addition of 5-Aminoindole/Tryptamine and Histamines onto Alkynes. J. Org. Chem. 2014, 79, 172-186.

(9) For selected recent reviews of hydroamination of alkynes, see: (a) Roh, S. W.; Choi, K.; Lee, C. Transition Metal Vinylidene- and Allenylidene-Mediated Catalysis in Organic Synthesis. Chem. Rev. 2019, 119, 4293−4356. (b) Huang, L.; Arndt, M.; Gooßen, K.; Heydt, H.; Gooßen, L. J. Late Transition Metal-Catalyzed Hydroamination and Hydroamidation. Chem. Rev. 2015, 115, 2596−2697. (c) Yim, J. C.-H.; Schafer, L. L. Efficient Anti-Markovnikov-Selective Catalysts for Intermolecular Alkyne Hydroamination: Recent Advances and Synthetic Applications. Eur. J. Org. Chem. 2014, 2014, 6825−6840. (d) Schafer, L. L.; Yim, J. C.-H.; Yonson, N. Transition-Metal- Catalyzed Hydroamination Reactions. In Metal-Catalyzed Cross-Coupling Reactions and More; de Meijere, A., Bräse, S., Oestreich, M., Eds.; Wiley-VCH: Weinheim, 2014; Vol. 3, pp 1135−1258. (e) Müller, T. E.; Hultzsch, K. C.; Yus, M.; Foubelo, F.; Tada, M. Hydroamination: Direct Addition of Amines to Alkenes and Alkynes. Chem. Rev. 2008, 108, 3795−3892.

(10) (a) Fukumoto, Y.; Asai, H.; Shimizu, M.; Chatani, N. Anti-Markovnikov Addition of Both Primary and Secondary Amines to Terminal Alkynes Catalyzed by the TpRh(C2H4)2/PPh3 System.J. Am. Chem. Soc. 2007, 129, 13792-13793. (b) Fukumoto, Y.; Kawahara, T.; Kanazawa, Y.; Chatani, N. Synthesis of (E)-3-Alkylidene-1-pyrrolines by the Rhodium-Catalyzed Cyclization of Terminal Alkynes with Homopropargylic Amines. Adv. Synth. Catal. 2007, 351, 2315-2318. (c) Fukumoto, Y.; Ohmae, A.; Hirano, M.; Chatani, N. Rhodium-Catalyzed Anti-Markovnikov Hydrohydrazination of Terminal Alkynes with N-Alkyl- and N,N-Dialkylhydrazines. Asian. J. Org. Chem. 2013, 2, 1036-1039.

(11) (a) Lam, R. H.; Walker, D. B.; Tucker, M. H.; Gatus, M. R. D.; Bhadhade, M.; Messerle, B. A.Intermolecular Hydroalkoxylation of Terminal Alkynes Catalyzed by a Dipyrrinato Rhodium(I)Complex with Unusual Selectivity. Organometallics 2015, 34, 4312-4317. (b) Sarbajna, A.; Pandey, P.; Rahaman, S. M. W.; Singh, K.; Tyagi, A.; Dixneuf, P. H.; Bera, J. K. A Triflamide- Tethered N-Heterocyclic Carbene–Rhodium(I) Catalyst for Hydroalkoxylation Reactions: Ligand-Promoted Nucleophilic Activation of Alcohols. ChemCatChem 2017, 9, 1397-1401. (c) see also ref 15 h.

(12) Tokunaga, M.; Wakatsuki, Y. The First Anti-Markovnikov Hydration of Terminal Alkynes: Formation of Aldehydes Catalyzed by a Ruthenium(II)/Phosphane Mixture. Angew. Chem. Int. Ed. 1998, 37, 2867-2869.

(13) Junting Chen, F. Y.; Ritter, T. Rh-Catalyzed Anti-Markovnikov Hydrocyanation of Terminal Alkynes. J. Am. Chem. Soc. 2017, 139, 7184-7187.

(14) (a) Tang, C. W.; VanSlyke, S. A. Organic electroluminescent diodes. Appl. Phys. Lett. 1987, 51, 913-915. (b) Tang, C. W.; VanSlyke, S. A.; Chen, C. K. Electroluminescence of doped organic thin films. J. Appl. Phys. 1989, 65, 3610-3616. Selected recent reviews, also see: (c) Bauri, J.; Choudhary, R. B.; Mandal, G. Recent advances in efficient emissive materials-based OLED applications: a review. J. Master. Sci. 2021, 56, 18837-18866. (d) Scholz, S.; Kondakov, D.; Lüssem, B.; Leo, K. Degradation Mechanisms and Reactions in Organic Light-Emitting Devices. Chem. Rev. 2015, 115, 8449-8503. (e)Thejokalyani, N.; Dhoble, S. J. Novel approaches for energy efficient solid state lighting by RGB organic light emitting diodes-A review. Renewable Sustainable Energy Rev. 2014, 32, 448-467.

(15) (a) Takano, S.; Shiomi, R.; Morimoto, Y.: Kochi, T.; Kakiuchi, F. Carbon–Carbon Bond Formation via Catalytically Generated Aminocarbene Complexes: Rhodium-Catalyzed Hydroaminative Cyclization of Enynes with Secondary Amines. Angew. Chem. Int. Ed. 2020, 59, 11754-11757. (b) Kakiuchi, F.; Takano, S.; Kochi, T. Catalytic Reactions of Terminal Alkynes Using Rhodium(I) Complexes Bearing 8-Quinolinolate Ligands. ACS Catal. 2018, 8, 6127-6137.(c) Takano, S.; Kochi, T.; Kakiuchi, F. Formation of α-Monosubstituted Propargylamines from Terminal Alkynes and Secondary Amines Using a (PNO)Rh/Cu Tandem Catalyst System. Chem. Lett. 2017, 46, 1620-1623. (d) Takano, S.; Kochi, T.; Kakiuchi, F. Synthesis and Reactivity of Phosphine-Quinolinolato Rhodium Complexes: Intermediacy of Vinylidene and (Amino)carbene Complexes in the Catalytic Hydroamination of Terminal Alkynes. Organometallics 2016, 35, 4112-4125. (e) Mochizuki, K.; Sakai, K.; Kochi, T.; Kakiuchi, F. Rhodium-Catalyzed Dimerization of Arylacetylenes and Addition of Malonates to 1,3-Enynes. Synthesis 2013, 45, 2088-2092. (f) Sakai, K.; Kochi, T.; Kakiuchi, F. Rhodium-Catalyzed Intermolecular [2 þ 2] Cycloaddition of Terminal Alkynes with Electron-Deficient Alkenes. Org. Lett. 2013, 15, 1024- 2027. (g) Sakai, K.; Kochi, T.; Kakiuchi, F. Rhodium-Catalyzed anti-Markovnikov Addition of Secondary Amines to Arylacetylenes at Room Temperature. Org.Lett. 2011, 13, 3928-3931. (h) Kondo, M.; Kochi, T.; Kakiuchi, F. Rhodium-Catalyzed Anti-Markovnikov IntermolecularHydroalkoxylation of Terminal Acetylenes. J. Am. Chem. Soc. 2011, 133, 32-34.

(16) Jaseer, E. A.; Casado, M. A.; Al-Saadi, A. A.; Oro, L. A. Intermolecular hydroamination versus stereoregular polymerization of phenylacetylene by rhodium catalysts based on N–O bidentate ligands. Inorg. Chem. Commun. 2014, 40, 78−81.

(17) Cowley, M. J.; Lynam, J. M.; Slattery, J. M. A mechanistic study into the interconversion of rhodium alkyne, alkynyl hydride and vinylidene complexes. Dalton Trans., 2008, 4552-4554.

本論 第 1 章

(18) (a) Haskel, A.; Straub, T.; Eisen, M. S. Organoactinide-Catalyzed Intermolecular Hydroamination of Terminal Alkynes. Organometallics 1996, 15, 3773-3775. (b) Straub, T.; Haskel, A.; Neyroud, T. G.; Kapon, M.; Botoshansky, M.; Eisen, M. S. Intermolecular Hydroamination of Terminal Alkynes Catalyzed by Organoactinide Complexes. Scope and Mechanistic Studies. Organometallics 2001, 20, 5017-5035.

(19) (a) Haak, E.; Siebeneicher, H.; Doye, S. An Ammonia Equivalent for the Dimethyltitanocene- Catalyzed Intermolecular Hydroamination of Alkynes. Org. Lett. 2000, 2, 1935-1937. (b) Heutling, A.; Pohlki, F.; Doye, S. [Ind2TiMe2]: A General Catalyst for the Intermolecular Hydroamination of Alkynes. Chem. Eur. J. 2004, 10, 3059-3071. (c) Brahms, C.; Tholen, P.; Saak, W.; Doye, S. An (Aminopyrimidinato)titanium Catalyst for the Hydroamination of Alkynes and Alkenes. Eur. J. Org. Chem. 2013, 7583-7592. (d) Haak, E.; Bytschkov, I.; Doye, S. Intermolecular Hydroamination of Alkynes Catalyzed by Dimethyltitanocene. Angew. Chem. Int. Ed. 1999, 38, 3389-3391. (e) Born, K.; Doye, S. Zirconium-Catalyzed Intermolecular Hydroamination of Alkynes with Primary Amines. Eur. J. Org. Chem. 2012, 764-771.

(20) (a) Tillack, A.; Garcia Castro, I.; Hartung, C. G.; Beller, M. Anti-Markovnikov Hydroamination of Terminal Alkynes. Angew. Chem. Int. Ed. 2002, 41, 2541-2543. (b) Tillack, A.; Jiao, H.; Garcia Castro, I.; Hartung, C. G.; Beller, M. A General Study of [(η5-Cp’)2Ti(η2-Me3SiC2SiMe3)]- Catalyzed Hydroamination of Terminal Alkynes: Regioselective Formation of Markovnikov and Anti-Markovnikov Products and Mechanistic Explanation (Cp’=C5H5, C5H4Et, C5Me5). Chem. Eur. J. 2004, 10, 2409-2420. (c) Tillack, A.; Khedkar, V.; Beller, M. Controlling selectivity: from Markovnikov to anti-Markovnikov hydroamination of alkynes. Tetrahedron Lett 2004, 45, 8875- 8878. (d) Tillack, A.; Khedkar, V.; Jiao, H.; Beller, M. A General Study of Aryloxo and Alkoxo Ligands in the Titanium-Catalyzed Intermolecular Hydroamination of Terminal Alkynes. Eur. J. Org. Chem. 2005, 5001-5012.

(21) (a) Zhang, Z.; Schafer, L. L. Anti-Markovnikov Intermolecular Hydroamination: A Bis(amidate) Titanium Precatalyst for the Preparation of Reactive Aldimines. Org. Lett. 2003, 5, 4733-4736.(b) Zhang, Z.; Leitch, D. C.; Lu, M.; Patrick, B. O.; Schafer, L. L. An Easy-To-Use, Regioselective,and Robust Bis(amidate) Titanium Hydroamination Precatalyst: Mechanistic and Synthetic Investigations toward the Preparation of Tetrahydroisoquinolines and Benzoquinolizine Alkaloids. Chem. Eur. J. 2007, 13, 2012-2022. (c) Yim, J. C.-H.; Bexrud, J. A.; Ayinla, R. O.; Leitch, D. C.;Schafer, L. L. Bis(amidate)bis(amido) Titanium Complex: A Regioselective Intermolecular Alkyne Hydroamination Catalyst. J. Org. Chem. 2014, 79, 2015-2028. (d) Lui, E. K. J.; Schafar,L. L. Facile Synthesis and Isolation of Secondary Amines via a Sequential Titanium(IV)- Catalyzed Hydroamination and Palladium-Catalyzed Hydrogenation. Adv. Synth. Catal. 2016, 358, 713-718.

(22) (a) Buil, M. L.; Esteruelas, M. A.; López, A. M.; Mateo, A. C.; Oñate, E. Preparation and X-ray Structures of Alkyl-Titanium(IV) Complexes Stabilized by Indenyl Ligands with a Pendant Ether or Amine Substituent and Their Use in the Catalytic Hydroamination of Alkynes. Organometallics 2007, 26, 554-565. (b) Buil, M. L.; Esteruelas, M. A.; López, A. M.; Mateo, A. C. Preparation of Half-Sandwich Alkyl-Titanium(IV) Complexes Stabilized by a Cyclopentadienyl Ligand with a Pendant Phosphine Tether and Their Use in the Catalytic Hydroamination of Aliphatic and Aromatic Alkynes. Organometallics 2006, 25, 4079- 4089. (c) Esteruelas, M. A.; López, A. M.; Mateo, A. C.; Oñate, E. New Half-Sandwich Alkyl, Aryl, Aryloxide, and Propargyloxide Titanium(IV) Complexes Containing a Cyclopentadienyl Ligand with a Pendant Ether Substituent: Behavior and Influence in the Hydroamination of Alkynes of the Ether Group. Organometallics 2006, 25, 1448-1460. (d) Esteruelas, M. A.; López, A. M.; Mateo, A. C.; Oñate,E. New Titanium Complexes Containing a Cyclopentadienyl Ligand with a Pendant Aminoalkyl Substituent: Preparation, Behavior of the Amino Group, and Catalytic Hydroamination of Alkynes. Organometallics 2005, 24, 5084-5094. (f) Ward, B. D.; Maisse-François, A.; Mountford, P.; Gade,L. H. Synthesis and structural characterization of an azatitanacyclobutene: the key intermediate in the catalytic anti-Markovnikov addition of primary amines to α-alkynes. Chem. Commun., 2004, 704-705.

第 2 章

(23) Alonso-Moreno, C.; Carrillo-Hermosilla, F.; Romero-Fernάndez, J.; Rodrίguez, A. M.; Otero, A.; Antiñolo, A. Well-Defined Regioselective Iminopyridine Rhodium Catalysts for Anti- Markovnikov Addition of Aromatic Primary Amines to 1-Octyne. Adv. Synth. Catal. 2009, 351, 881-890.

(24) Basicity of organic bases, see: (a) Schwesinger, R.; Schlemper, H.; Hasenfratz, C.; Willaredt, J.; Dambacher, T.; Breuer, T.; Ottaway, C.; Fletschinger, M.; Boele, J.; Fritz, H.; Putzas, D.; Rotter,H. W.; Bordwell, F. G.; Satish, A. V.; Ji, G.-Z.; Peters, E.-M.; Peters, K.; von Schnering, H. G.; Walz, L. Extremely Strong, Uncharged Auxiliary Bases; Monomeric and Polymer-Supported Polyaminophosphazenes (P2-P5). Liebigs Ann. 1996, 1055−1081. (b) Schwesinger, R.; Willaredt,J.; Schlemper, H.; Keller, M.; Schmitt, D.; Fritz, H. Novel, Very Strong, Uncharged Auxiliary Bases; Design and Synthesis of Monomeric and Polymer-Bound Triaminoiminophosphorane Bases of Broadly Varied Steric Demand. Chem. Ber. 1994, 127, 2435−2454. (c) Kolthoff, I. M.; Chantooni, M. K.; Bhowmik, S. Dissociation Constants of Uncharged and Monovalent Cation Acids in Dimethyl Sulfoxide. J. Am. Chem. Soc. 1968, 90, 23−28. (d) Tshepelevitsh, S.; Kütt, A.; Lõkov, M.; Kaljurand, I.; Saame, J.; Heering, A.; Plieger, P. G.; Vianello, R.; Leito, I. On the Basicity of Organic Bases in Different Media. Eur. J. Org. Chem. 2019, 2019, 6735−6748. (e) Benoit, R. L.; Lefebvre, D.; Fréchette, M. Basicity of 1,8-bis(dimethylamino)naphthalene and 1,4- diazabicyclo[2.2.2]octane in water and dimethylsulfoxide. Can. J. Chem. 1987, 65, 996-1001. (f) Coetzee, J. F.; Padmanabhan, G. R. Properties of Bases in Acetonitrile as Solvent. IV. Proton Acceptor Power and Homoconjugation of Mono- and Diamines. J. Am. Chem. Soc. 1965, 87, 5005-5010. (g) Kaljurand, I.; Rodima, T.; Leito, I.; Koppel, I. A.; Schwesinger, R. Self-Consistent Spectrophotometric Basicity Scale in Acetonitrile Covering the Range between Pyridine and DBU.J. Org. Chem. 2000, 65, 6202-6208. (h) Kaljurand, I.; Kütt, A.; Sooväli, L.; Rodima, T.; Mäemets, V.; Leito, I.; Koppel, I. A. Extension of the Self-Consistent Spectrophotometric Basicity Scale in Acetonitrile to a Full Span of 28 pKa Units: Unification of Different Basicity Scales. J. Org. Chem. 2005, 70, 1019− 1028. (i) Benoit, R. L.; Fréchette, M.; Lefebvre, D. 2,6-Di-tert-butylpyridine: an unusually weak base in dimethylsulfoxide. Can. J. Chem. 1988, 66, 1159−1162.

第 3 章

(25) (a) Heyl, F. W.; Herr, M. E. “Enamine” Derivatives of Steroidal Carbonyl Compounds. J. Am. Chem. Soc. 1953, 75, 1918-1920. (b) Stork, G.; Terrell, R.; Szmuszkovicz, J. A new synthesis of 2-alkyl and 2-acylketones. J. Am. Chem. Soc. 1954, 76, 2029-2030.

(26) (a) Leitch, D. C.; Payne, P. R.; Dunbar, C. R.; Schafer, L. L. Broadening the Scope of Group 4 Hydroamination Catalysis Using a Tethered Ureate Ligand. J. Am. Chem. Soc. 2009, 131, 18246- 18247. (b) Leitch, D. C.; Turner, C. S.; Schafer, L. L. Isolation of Catalytic Intermediates in Hydroamination Reactions: Insertion of Internal Alkynes into a Zirconium–Amido Bond. Angew. Chem., Int. Ed. 2010, 49, 6382− 6386.

(27) Kocięcka, P.; Czeluśniak, I.; Szymańska-Buzar, T. Efficient and Selective Synthesis of E- Vinylamines via Tungsten(0)-Catalyzed Hydroamination of Terminal Alkynes. Adv. Synth. Catal. 2014, 356, 3319-3324.

(28) (a) Cheung, H. W.; So, C. M.; Pun, K. H.; Zhou, Z.; Lau, C. P. Hydro(trispyrazolyl)borato- Ruthenium(II) Diphosphinoamino Complex-Catalyzed Addition of β-Diketones to 1-Alkynes and Anti-Markovnikov Addition of Secondary Amines to Aromatic 1-Alkynes. Adv. Synth. Catal. 2011, 353, 411-425. (b) see ref 16 (c) Bahri, J.; Blieck, R.; Jamoussi, B.; Taillefer, M.; Monnier,F. Hydroamination of terminal alkynes with secondary amines catalyzed by copper: regioselective access to amines. Chem. Commun., 2015, 51, 11210− 11212.

(29) Park, Y. J.; Kwon, B.-II.; Ahn, J.-A.; Lee, H.; Jun, C.-H. Chelation-Assisted Hydrative Dimerization of 1-Alkyne Forming α,β-Enones by an Rh(I) Catalyst. J. Am. Chem. Soc. 2004, 126, 13892-13893.

(30) Synthesis of Propargylamines, see: (a) Gardner, C.; Kerrigan, V.; Rose, J. D.; Weedon, B. C. L. Acetylene Reactions. Part I. Aminobutynes from Acetylene and Primary or Secondary Amines. J. Chem. Soc. 1949, 780-782. (b) Kruse, C. W.; Kleinschmidt, R. F. N,N-Dialkyl-l,l-dimethyl-2- butynylamines by the Reaction of Propyne with Secondary Aliphatic Amines. J. Am. Chem. Soc. 1961, 83, 216-220. (c) Zhau, L.; Jiang, H.-f.; Li, C.-J. Efficient Synthesis of γ,δ-Alkynyl-β-amino Acid Derivatives by a New Copper-Catalyzed Amine-Alkyne-Alkyne Addition Reaction. Adv. Synth. Catal. 2008, 350, 2226-2230. (d) Zhou, L.; Shuai, Q.; Jiang, H.-f.; Li, C.-J. Copper- Catalyzed Amine–Alkyne–Alkyne Addition Reaction: An Efficient Method For the Synthesis of γ,δ-Alkynyl-β-amino Acid Derivatives. Chem. Eur. J. 2009, 15, 11668-11674. (e) Zhou, L.; Bohle,D. S.; Jiang, H.-F.; Li, C.-J. Synthesis of Propargylamines by a Copper-Catalyzed Tandem Anti- Markovnikov Hydroamination and Alkyne Addition. Synlett 2009, 6, 937-940. (f) Han, J.; Xu, B.; Hammond, G. B. Highly Efficient Cu(I)-Catalyzed Synthesis of N-Heterocycles through a Cyclization-Triggered Addition of Alkynes. J. Am. Chem. Soc. 2010, 132, 916-917. (g) Biyikal, M.; Porta, M.; Roesky, P. W.; Blechert, S. Zinc-Catalyzed Domino Hydroamination–Alkyne Addition. Adv. Synth. Catal. 2010, 352, 1870-1875. (h) Pierce, C. J.; Yoo, H.; Larsen, C. H. A Unique Route to Tetrasubstituted Propargylic Amines by Catalytic Markovnikov Hydroamination–Alkynylation. Adv. Synth. Catal. 2013, 355, 3586-3590. (i) Palchak, Z. L.; Lussier, D. J.; Pierce, C. J.; Yoo, H.; Larsen, C. H. Catalytic Tandem Markovnikov Hydroamination–Alkynylation and Markovnikov Hydroamination–Hydrovinylation. Adv. Synth. Catal. 2015, 357, 539-548. (j) Periasamy, M.; Reddy, P. O.; Satyanarayana, I.; Mohan, L.; Edukondalu, A. Diastereoselective Synthesis of Tetrasubstituted Propargylamines via Hydroamination and Metalation of 1-Alkynes and Their Enantioselective Conversion to Trisubstituted Chiral Allenes. J. Org. Chem. 2016, 81, 987-999. (k) see also ref 15c.

(31) Fukumoto, Y.; Kinashi, F.; Kawahara, T.; Chatani, N. Rhodium-Catalyzed Reaction of Terminal Alkynes with Allylamine Leading to (E)-3-Alkylidene N-Heterocycles. Org. Lett. 2006, 8, 4641- 4643.

(32) Reyes-Sánchez, A.; García-Ventura, I.; García, J. J. Easily available nickel complexes as catalysts for the intermolecular hydroamination of alkenes and alkynes. Dalton Trans., 2014, 43, 1762-1768.

(33) Bahri, J.; Jamoussi, B.; van Der Lee, A.; Taillefer, M.; Monnier, F. Copper-Catalyzed Hydroamination of Alkynes with Aliphatic Amines: Regioselective Access to (1E,3E)-1,4- Disubstituted-1,3-dienes. Org. Lett. 2015, 17, 1224-1227.

(34) Kim, H.; Lee, C. Rhodium-Catalyzed Cycloisomerization of N-Propargyl Enamine Derivatives.J. Am. Chem. Soc. 2006, 128, 6336-6337.

(35) Zhao, L.; Zhang, L.; Fang, D.-C. DFT Study on Rhodium-Catalyzed Intermolecular [2 + 2]Cycloaddition of Terminal Alkynes with Electron-Deficient Alkenes. Organometallics 2016, 35, 3577-3586.

第 4 章

(36) Selected recent review, see: Filho, J. F. A.; Lemos, B. C.; de Souza, A. S.; Pinheiro, S.; Greco, S.J. Multicomponent Mannich reactions: General aspects, methodologies and applications.Tetrahedron 2017, 73, 6977−7004.

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