过渡金属催化的导向碳氢键活化反应研究
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摘要
过渡金属催化的碳氢键活化反应由于具其有良好的原子经济性、环境友好而受到人们的广泛关注。近年来,对于碳氢键活化反应的研究方兴未艾,而且碳氢活化反应也逐渐被应用到天然产物、药物分子及功能材料的合成上,大大缩短了反应的步骤,提高了反应的产率。目前对于碳氢键活化反应的研究主要分为两类：一类是直接的碳氢键活化即在过渡金属的催化下对含有活性较高的碳氢键进行活化；第二类是通过引入导向基团高区域选择性的实现碳氢键官能化。本论文主要围绕过渡金属催化的导向碳氢键活化反应开展研究,主要内容包括：
1.铑催化的酯基导向的丙烯酸酯类化合物的碳氢烯基化反应
发展了铑催化的酯基导向的sp2碳氢烯基化反应——高选择性合成1,3-二烯类化合物。各种苯乙烯均可以与2-芳基丙烯酸酯反应生成1,4-二芳基取代的1,3-二烯类化合物,而且当使用丙烯酸乙酯作为偶联试剂时,反应高立体选择性的得到单一目标产物。通过对产物进行单晶培养和单晶解析,确定其主要为(Z,E)型结构。反应机理的研究发现该反应碳氢键活化是一个可逆过程而且氘代实验排除了金属经氧化加成活化碳氢键的历程。
2.铑催化的酯基导向的炔烃氢芳基化反应及多芳基取代萘酚类化合物的合成
发展了铑催化的酯基导向的sp2碳氢键活化反应,通过条件控制可以选择性的实现炔烃氢芳基化反应得到苯酚衍生物邻位烯基化的产物及多步碳氢键活化得到多芳基取代萘酚类化合物。各种酚类衍生物均可以与二苯乙炔反应生成相应的烯基化产物和多芳基取代萘酚化合物,该反应的发现为合成具有II-共轭体系的新型功能材料提供了一种方法。
3.钯催化的N,N-二甲氨基导向的碳氢键活化芳基化反应
发展了钯催化的N,N-二甲氨基导向的sp2碳氢键活化芳基化反应。通过底物取代基的调控可以选择性的得到单芳基化或双芳基化的产物。各种碘苯均可以与N,N-二甲基芐胺反应得到目标化合物。在对反应的条件探索时,发现乙酸铜的加入可以大大提高反应的产率。通过合成反应可能经历的中间体对反应机理进行了探索,发现乙酸和乙酸铜可以共同促进反应的进行,而且XRD谱图分析发现银离子在反应中主要起到夺取碘离子的作用。
4.钯催化的基于双导向的sp3碳氢键活化反应研究——高效合成3-位取代的脯氨酸
发展了钯催化的脯氨酸3-位碳氢键官能化反应。通过在脯氨酸上引入保护基团和导向基团实现脯氨酸3-位的碳氢键芳基化及烷基化反应。各种碘代芳烃均可以与保护的脯氨酸反应以较高的产率得到相应3-位芳基取代的产物,而且改变反应的条件溴苯亦可以与其反应生成相应的目标化合物。另外碘代苯乙烯和溴代乙酸乙酯也可以作为偶联试剂与底物反应分别生成脯氨酸3-位烯基化和烷基化的产物。通过对底物的导向基团和保护基团的脱除得到了3-芳基取代的脯氨酸而且利用该方法实现了一种单氨基再攫取抑制剂的合成。
Transition-Metal-Catalyzed C-H activation has become the most powerful and straightforward tool in synthetic chemistry because its highly efficient and atom-economic organic transformations for the construction of complex molecules. In recent years, many efforts have been focused on the application of the C-H bond activation and a lot of natural products and pharmaceutical moleculars have been synthesized using this method. The study of the C-H bond activation could be devided into two issues:(1) the direct C-H bond activation which is aimed at more acidic C-H bond;(2) the directed C-H bond activation which need a directing group to coordinate with the metal. This dissertation mainly focused on the studies of the directed C-H bond activation, the contents are as following:
1. Ester directed selective olefination of acrylates by rhodium-catalysis
Ester directed olefination of acrylates via rhodium(III)-catalyzed was developed. Various alkenes were reacted with acrylates to give desired products in high stereoselectivity. The X-ray spectra of the product conformed its structure. Mechanistic investigation revealed that ester directed C-H bond activation was the key-step to this reaction.
2. Ester directed selective hydroarylation of alkynes and synthesis of aryl-substituted naphthols via rhodium-catalysis
Ester directed olefination and cyclization of phenol derivative was developed. Different products could be detected when the reaction condition was changed. Alkynes with electron-withdrawing and electon-donation group could react with phenol derivative to give the alkenyl products when acetic acid and acetic anhydride existed.
3. N, N-dimethylaminomethyl group directed C-H ortho-arylation of arenes via palladium-catalysis
A novel protocol for palladium-catalyzed arylation of C(sp2)-H bond directed by N,N-dimethylaminomethyl group in the presence of AgOAc and Cu(OAc)2?H2O is described. Various aryl iodides proved to be efficient coupling partners, furnishing the corresponding ortho monoarylated or diarylated arenes in moderate to good yields. Cu(OAc)2?H2O is found to be the important additive to improve the yields in this transformation. The sepctra of XRD revealed that Ag (I) may play the role of abstraction halide.
4. Palladium-catalyzed bidentate-assisted sp3C-H functionalization:highly efficient to synthesize3-substituted proline
Regio-and diastereoselective arylation of prolines using Pd-catalyzed C(sp3)-H activation has been investigated. Prolines can be directly arylated in C3-position in moderate to high yields with a variety of (hetero)aryl iodides and bromides to give the optically pure proline derivatives, which are important units in many biologically active compounds and useful precursors in a variety of functional group transformations. The directing and protected group could be removed to give3-substituted prolines.
1.铑催化的酯基导向的丙烯酸酯类化合物的碳氢烯基化反应
发展了铑催化的酯基导向的sp2碳氢烯基化反应——高选择性合成1,3-二烯类化合物。各种苯乙烯均可以与2-芳基丙烯酸酯反应生成1,4-二芳基取代的1,3-二烯类化合物,而且当使用丙烯酸乙酯作为偶联试剂时,反应高立体选择性的得到单一目标产物。通过对产物进行单晶培养和单晶解析,确定其主要为(Z,E)型结构。反应机理的研究发现该反应碳氢键活化是一个可逆过程而且氘代实验排除了金属经氧化加成活化碳氢键的历程。
2.铑催化的酯基导向的炔烃氢芳基化反应及多芳基取代萘酚类化合物的合成
发展了铑催化的酯基导向的sp2碳氢键活化反应,通过条件控制可以选择性的实现炔烃氢芳基化反应得到苯酚衍生物邻位烯基化的产物及多步碳氢键活化得到多芳基取代萘酚类化合物。各种酚类衍生物均可以与二苯乙炔反应生成相应的烯基化产物和多芳基取代萘酚化合物,该反应的发现为合成具有II-共轭体系的新型功能材料提供了一种方法。
3.钯催化的N,N-二甲氨基导向的碳氢键活化芳基化反应
发展了钯催化的N,N-二甲氨基导向的sp2碳氢键活化芳基化反应。通过底物取代基的调控可以选择性的得到单芳基化或双芳基化的产物。各种碘苯均可以与N,N-二甲基芐胺反应得到目标化合物。在对反应的条件探索时,发现乙酸铜的加入可以大大提高反应的产率。通过合成反应可能经历的中间体对反应机理进行了探索,发现乙酸和乙酸铜可以共同促进反应的进行,而且XRD谱图分析发现银离子在反应中主要起到夺取碘离子的作用。
4.钯催化的基于双导向的sp3碳氢键活化反应研究——高效合成3-位取代的脯氨酸
发展了钯催化的脯氨酸3-位碳氢键官能化反应。通过在脯氨酸上引入保护基团和导向基团实现脯氨酸3-位的碳氢键芳基化及烷基化反应。各种碘代芳烃均可以与保护的脯氨酸反应以较高的产率得到相应3-位芳基取代的产物,而且改变反应的条件溴苯亦可以与其反应生成相应的目标化合物。另外碘代苯乙烯和溴代乙酸乙酯也可以作为偶联试剂与底物反应分别生成脯氨酸3-位烯基化和烷基化的产物。通过对底物的导向基团和保护基团的脱除得到了3-芳基取代的脯氨酸而且利用该方法实现了一种单氨基再攫取抑制剂的合成。
Transition-Metal-Catalyzed C-H activation has become the most powerful and straightforward tool in synthetic chemistry because its highly efficient and atom-economic organic transformations for the construction of complex molecules. In recent years, many efforts have been focused on the application of the C-H bond activation and a lot of natural products and pharmaceutical moleculars have been synthesized using this method. The study of the C-H bond activation could be devided into two issues:(1) the direct C-H bond activation which is aimed at more acidic C-H bond;(2) the directed C-H bond activation which need a directing group to coordinate with the metal. This dissertation mainly focused on the studies of the directed C-H bond activation, the contents are as following:
1. Ester directed selective olefination of acrylates by rhodium-catalysis
Ester directed olefination of acrylates via rhodium(III)-catalyzed was developed. Various alkenes were reacted with acrylates to give desired products in high stereoselectivity. The X-ray spectra of the product conformed its structure. Mechanistic investigation revealed that ester directed C-H bond activation was the key-step to this reaction.
2. Ester directed selective hydroarylation of alkynes and synthesis of aryl-substituted naphthols via rhodium-catalysis
Ester directed olefination and cyclization of phenol derivative was developed. Different products could be detected when the reaction condition was changed. Alkynes with electron-withdrawing and electon-donation group could react with phenol derivative to give the alkenyl products when acetic acid and acetic anhydride existed.
3. N, N-dimethylaminomethyl group directed C-H ortho-arylation of arenes via palladium-catalysis
A novel protocol for palladium-catalyzed arylation of C(sp2)-H bond directed by N,N-dimethylaminomethyl group in the presence of AgOAc and Cu(OAc)2?H2O is described. Various aryl iodides proved to be efficient coupling partners, furnishing the corresponding ortho monoarylated or diarylated arenes in moderate to good yields. Cu(OAc)2?H2O is found to be the important additive to improve the yields in this transformation. The sepctra of XRD revealed that Ag (I) may play the role of abstraction halide.
4. Palladium-catalyzed bidentate-assisted sp3C-H functionalization:highly efficient to synthesize3-substituted proline
Regio-and diastereoselective arylation of prolines using Pd-catalyzed C(sp3)-H activation has been investigated. Prolines can be directly arylated in C3-position in moderate to high yields with a variety of (hetero)aryl iodides and bromides to give the optically pure proline derivatives, which are important units in many biologically active compounds and useful precursors in a variety of functional group transformations. The directing and protected group could be removed to give3-substituted prolines.
引文
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2. For examples, see:(a) Daugulis, O.; Zaitsev, V. G., Anilide ortho-Arylation by Using C-H Activation Methodology. Angew. Chem., Int. Ed. 2005, 44 (26), 4046-4048. (b) Li, B.-J.; Tian, S.-L.; Fang, Z.; Shi, Z.-J., Multiple C-H Activations To Construct Biologically Active Molecules in a Process Completely Free of Organohalogen and Organometallic Components. Angew. Chem., Int. Ed.2008,47 (6), 1115-1118. (c) Wasa, M.; Engle, K. M., Yu, J.-Q., Pd(0)/PR3-Catalyzed Intermolecular Arylation of sp3 C-H Bonds. J. Am. Chem. Soc.2009,131 (29), 9886-9887. (d) Nishikata, T.; Abela, A. R.; Huang, S.; Lipshutz, B. H., Cationic palladium(II) catalysis:C-H activation/Suzuki-Miyaura couplings at room temperature. J. Am. Chem. Soc. 2010,132 (14),4978-4979. (e) Zhao, X.; Yeung, C. S.; Dong, V. M., Palladium-Catalyzed Ortho-Arylation of O-Phenylcarbamates with Simple Arenes and Sodium Persulfate. J. Am. Chem. Soc.2010,132 (16),5837-5844. (f) Wencel-Delord, J.; Nimphius, C.;Patureau, F. W.; Glorius, F., [RhⅢCp*]-Catalyzed Dehydrogenative Aryl-Aryl Bond Formation. Angew Chem., Int. Ed. 2012,51 (9), 2247-2251. (g) Peter Tsang, W. C.; Zheng, N.; Buchwald, S. L., Combined C-H Functionalization/C-N Bond Formation Route to Carbazoles. J. Am. Chem. Soc.2005, 127 (42),14560-14561. (h) Li, D.-D.; Yuan, T.-T.; Wang, G.-W., Palladium-Catalyzed ortho-Arylation of Benzamides via Direct sp2 C-H Bond Activation. J. Org. Chem. 2012,77 (7), 3341-3347. (i) Peron, F.; Fossey, C.; Cailly, T.; Fabis, F., N-Tosylcarboxamide as a Transformable Directing Group for Pd-Catalyzed C-H ortho-Arylation. Org. Lett.2012,14 (7),1827-1829.
3. (a) Colby, D. A.; Bergman, R. G.; Ellman, J. A., Stereoselective Alkylation of a, β-Unsaturated Imines via C-H Bond Activation. J. Am. Chem. Soc. 2006,128 (17), 5604-5605. (b) Colby, D. A.; Bergman, R. G.; Ellman, J. A., Synthesis of Dihydropyridines and Pyridines from Imines and Alkynes via C-H Activation. J. Am. Chem. Soc. 2008,130 (11),3645-3651. (c) Parthasarathy, K.; Jeganmohan, M. Cheng, C.-H., Rhodium-Catalyzed One-Pot Synthesis of Substituted Pyridine Derivatives from α,β-Unsaturated Ketoximes and Alkynes. Org. Lett.2008,10 (2),325-328. (d) Guimond, N.; Fagnou, K., Isoquinoline Synthesis via Rhodium-Catalyzed Oxidative Cross-Coupling/Cyclization of Aryl Aldimines and Alkynes. J. Am. Chem. Soc.2009, 131 (34),12050-12051. (e) Ding, S.; Shi, Z.; Jiao, N., Pd(Ⅱ)-Catalyzed Synthesis of Carbolines by Iminoannulation of Internal Alkynes via Direct C-H Bond Cleavage Using Dioxygen as Oxidant. Org. Lett. 2010,12 (7).1540-1543. (f) Too, P. C.; Wang, Y. F.; Chiba, S., Rhodium(Ⅲ)-Catalyzed Synthesis of Isoquinolines from Aryl Ketone O-Acyloxime Derivatives and Internal Alkynes. Org. Lett. 2010,12 (24),5688-5691. (g) Chinnagolla, R. K.; Pimparkar, S.; Jeganmohan, M., Ruthenium-Catalyzed Highly Regioselective Cyclization of Ketoximes with Alkynes by C-H Bond Activation:A Practical Route to Synthesize Substituted Isoquinolines. Org. Lett.2012,14 (12), 3032-3035. (h) Lian, Y.; Huber, T.; Hesp, K.; Bergman, R. G.; Ellman, J. A., Rhodium(III)-Catalyzed Alkenyl C-H Bond Functionalization:Convergent Synthesis of Furans and Pyrroles. Angew. Chem., Int. Ed.2013,52 (2),629-633.
4. (a) Satoh, T.; Kawamura, Y.; Miura, M.; Nomura, M., Palladium-Catalyzed Regioselective Mono- and Diarylation Reactions of 2-Phenylphenols and Naphthols with Aryl Halides. Angew. Chem., Int. Ed.1997,36 (16),1740-1742. (b) Kawamura, Y.; Satoh, T.; Miura, M.; Nomura M., Multiple Arylation of Phenols around the Oxygen under Palladium Catalysis. Chem. Lett.1999,961-962. (c) Terao, Y.; Nomoto, M.; Satoh, T.; Miura, M.; Nomura, M., Palladium-Catalyzed Dehydroarylation of Triarylmethanols and Their Coupling with Unsaturated Compounds Accompanied by C-C Bond Cleavage. J. Org. Chem.2004,69 (20),6942-6944. (d) Wakui, H.; Kawasaki, S.; Satoh, T.; Miura, M.; Nomura, M., Palladium-Catalyzed Reaction of 2-Hydroxy-2-methylpropiophenone with Aryl Bromides:A Unique Multiple Arylation via Successive C-C and C-H Bond Cleavages. J. Am. Chem. Soc.2004,126 (28),8658-8659. (e) Lu, Y.; Wang, D.-H.; Engle, K. M.; Yu, J.-Q., Pd(Ⅱ)-Catalyzed Hydroxyl-Directed C-H Olefination Enabled by Monoprotected Amino Acid Ligands. J. Am. Chem. Soc.2010,132 (16),5916-5921. (f) Lu, Y.; Leow, D.; Wang, X.; Engle, K. M.; Yu, J.-Q., Hydroxyl-directed C-H carbonylation enabled by mono-N-protected amino acid ligands:An expedient route to 1-isochromanones. Chem. Sci.2011,2, 967-971. (g) Huang, C.; Chattopadhyay, B.; Gevorgyan, V., Silanol:A Traceless Directing Group for Pd-Catalyzed o-Alkenylation of Phenols. J. Am. Chem. Soc.2011, 133 (32),12406-12409. (h) Morimoto, K.; Hirano, K.; Satoh, T.; Miura, M., Synthesis of Isochromene and Related Derivatives by Rhodium-Catalyzed Oxidative Coupling of Benzyl and Allyl Alcohols with Alkynes. J. Org. Chem.2011,76 (22),9548-9551.
5. (a) Garcia-Rubia, A.; Arrayas, R. G.; Carretero, J. C., Palladium(II)-Catalyzed Regioselective Direct C2 Alkenylation of Indoles and Pyrroles Assisted by the N-(2-Pyridyl)sulfonyl Protecting Group. Angew. Chem. Int. Ed.2009,48 (35), 6511-6515. (b) Garcia-Rubia, A.; Urones, B.; Arrayas, R. G.; Carretero, J. C. PdⅡ-Catalyzed C-H Olefination of N-(2-Pyridyl)sulfonyl Anilines and Arylalkylamines. Angew. Chem. Int. Ed.2011, 50 (46),10927-10931. (c) Garcia-Rubia, A.; Fernandez-Ibanez, M. A.; Arrayas, R. G.; Carretero, J. C.,2-Pyridyl Sulfoxide:A Versatile and Removable Directing Group for the PdⅡ-Catalyzed Direct C-H Olefination of Arenes. Chem. Eur. J.2011,17 (13),3567-3570. (d) Yu, M.; Liang, Z.; Wang, Y.; Zhang, Y, Palladium(Ⅱ)-Catalyzed Direct Alkenylation and Arylation of Arenes:Removable 2-Pyridylsulfinyl Group Assisted C-H Bond Activation. J. Org. Chem.2011,76 (12),4987-4994. (e) Romero-Revilla, J. A.; Garcia-Rubia, A.; Arrayas R. G.; Fernandez-Ibanez, M. A.; Carretero, J. C., Palladium-catalyzed coupling of arene C-H bonds with methyl- and arylboron reagents assisted by the removable 2-pyridylsulfinyl group. J. Org. Chem.2011,76 (22),9525-9530. (f) Zhang, X.; Yu, M.; Yao, J.; Zhang, Y., Palladium-Catalyzed Regioselective Arylation of Arene C-H Bond Assisted by the Removable 2-Pyridylsulfinyl Group. Synlett 2012, 23,463-467.
6. (a) Yu, M.; Xie, Y.; Xie, C.; Zhang, Y, Palladium-Catalyzed C-H Alkenylation of Arenes Using Thioethers as Directing Group. Org. Lett.2012,14 (8),2164-2167. (b) Yao, J.; Yu, M.; Zhang, Y., Thioethers as Directing Group for the Palladium-Catalyzed Direct Arylation of Arenes. Adv. Synth. Catal.2012,354, 3205-3210. (c) Zhang, X.-S.;Zhu, Q.-L.; Zhang, Y.F.; Li, Y.-B.; Shi, Z.-J., Controllable Mono-/Dialkenylation of Benzyl Thioethers through Rh-Catalyzed Aryl C-H Activation. Chem. Eur. J.2013,19(36),11898-11903.
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9. (a) Shan, G.; Yang, X.; Ma, L.; Rao, Y, Pd-Catalyzed C-H Oxygenation with TFA/TFAA:Expedient Access to Oxygen-Containing Heterocycles and Late-Stage Drug Modification. Angeu:Chem., Int. Ed.2012,51 (52),13070-13074. (b) Yang, Y.; Lin, Y.; Rao, Y., Ruthenium(Ⅱ)-Catalyzed Synthesis of Hydroxylated Arenes with Ester as an Effective Directing Group. Org. Lett.2012,14 (11),2874-2877. (c) Shan, G.; Han, X.; Lin, Y.; Yu, S.; Rao, Y., Broadening the Catalyst and Reaction Scope of Regio-and Chemoselective C-H Oxygenation:A Convenient and Scalable Approach to 2-Acylphenols by Intriguing Rh(Ⅱ) and Ru(Ⅱ) Catalysis. Org. Biomol. Chem.2013, 11,2318-2322. (d) Sun, X.; Shan, G.; Sun, Y.; Rao, Y., Regio- and Chemoselective C-H Chlorination/Bromination of Electron-Deficient Arenes by Weak Coordination and Study of Relative Directing-Group Abilities. Angew. Chem., Int. Ed.2013,52 (16),4440-4444.
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3. For selected general reviews of transition-metal-catalyzed C-H activation and its synthetic applications, see:(a) Alberico, D.; Scott, M. E.; Lautens, M., Aryl-Aryl Bond Formation by Transition-Metal-Catalyzed Direct Arylation. Chem. Rev.2007, 107 (1),174-238. (b) Chen, X.; Engle, K. M.; Wang, D.-H.; Yu, J.-Q., Palladium(II)-Catalyzed C-H Activation/C-C CrossCoupling Reactions:Versatility and Practicality. Angew. Chem.. Int. Ed.2009,48 (28),5094-5115. (c) Ackermann, L. Vicente, R.; Kapdi, A. R., Transition-metal-catalyzed direct arylation of (hetero)arenes by C-H bond cleavage. Angew. Chem.. Int. Ed.2009,48 (52), 9792-9826. (d) Lyons, T. W.; Sanford, M. S., Palladium-Catalyzed Ligand-Directed C-H Functionalization Reactions. Chem. Rev.2010,110 (2),1147-1169. (e) Jazzar, R. Hitce, J.; Renaudat, A., Sofack-Kreutzer, J., Baudoin, O., Functionalization of Organic Molecules by Transition-Metal-Catalyzed C(sp3)-H Activation. Chem. Eur. J. 2010,16 (9),2654-2672. (f) Yeung, C. S., Dong, V. M., Catalytic Dehydrogenative Cross-Coupling:Forming Carbon-Carbon Bonds by Oxidizing Two Carbon-Hydrogen Bonds. Chem. Rev.2011,111 (3),1251-1292. (g) Magano, J., Dunetz, J. R., Large-Scale Applications of Transition Metal-Catalyzed Couplings for the Synthesis of Pharmaceuticals. Chem. Rev.2011,111 (3),2177-2250.
4. Song, G.; Wang, F.; Li, X., C-C, C-O and C-N bond formation via Rhodium(III)-Catalyzed Oxidative C-H activation. Chem. Soc. Rev.2012,41, 3651-3678.
5. Umeda, N.; Tsurugi, H.; Satoh, T.; Miura, M., Fluorescent Naphthyl- and Anthrylazoles from the Catalytic Coupling of Phenylazoles with Internal Alkynes through the Cleavage of Multiple C-H Bonds. Angew. Chem.. Int. Ed.2008,47 (21), 4019-4022.
6. Schipper, D.; Hutchinson, M.; Fagnou, K., Rhodium(Ⅲ)-Catalyzed Intermolecular Hydroarylation of Alkynes. J. Am. Chem. Soc.2010,132 (20),6910-6911.
7. (a) Guimond, N.; Fagnou, K., Isoquinoline Synthesis via Rhodium-Catalyzed Oxidative Cross-Coupling/Cyclization of Aryl Aldimines and Alkynes. J. Am. Chem. Soc.2009,131 (34),12050-12051. (b) Guimond, N.; Gouliaras, C.; Fagnou, K., Rhodium(III)-Catalyzed Isoquinolone Synthesis:The N-O Bond as a Handle for C-N Bond Formation and Catalyst Turnover. J. Am. Chem. Soc.2010,132 (20),6908-6909. (c) Guimond, N.; Gorelsky, S. I. Fagnou, K., Rhodium(Ⅲ)-Catalyzed Heterocycle Synthesis Using an Internal Oxidant:Improved Reactivity and Mechanistic Studies. J. Am. Chem. Soc.2011,133 (16),6449-6457.
8. Mochida, S.; Umeda, N.; Hirano, K.; Satoh, T.; Miura, M., Rhodium-catalyzed Oxidative Coupling/Cyclization of Benzamides with Alkynes via C-H Bond Cleavage. Chem. Lett.2010,39,744-746.
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12. (a) Colby, D. A.; Bergman, R. G.; Ellman, J. A., Synthesis of Dihydropyridines and Pyridines from Imines and Alkynes via C-H Activation. J. Am. Chem. Soc.2008, 130 (11),3645-3651. (b) Parthasarathy, K.; Jeganmohan, M. Cheng, C-H., Rhodium-Catalyzed One-Pot Synthesis of Substituted Pyridine Derivatives from a, β-Unsaturated Ketoximes and Alkynes. Org. Lett.2008,10 (2),325-328. (c) Too, P. C.; Wang, Y. F.; Chiba, S., Rhodium(Ⅲ)-Catalyzed Synthesis of Isoquinolines from Aryl Ketone O-Acyloxime Derivatives and Internal Alkynes. Org. Lett.2010,12 (24), 5688-5691.
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111. (a) Zhang, S.-Y.; Li, Q.; He, G.; Nack, W. A.; Chen, G., Stereo selective Synthesis of β-Alkylated α-Amino Acids via Palladium-Catalyzed Alkylation of Unactivated Methylene C(sp3)-H Bonds with Primary Alkyl Halides. J. Am. Chem. Soc.2013,135 (32),12135-12141. (b) Chen, K.; Hu, R.; Zhang, S.-Q.; Shi, B.-F., Pd(Ⅱ)-Catalyzed Alkylation of Unactivated C(sp3)-H Bonds:Efficient Synthesis of Optically Active Unnatural a-Amino Acids. Chem. Sci.2013,4,3906.
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1. For selected general reviews of transition-metal-catalyzed C-H activation and its synthetic applications, see:(a) Alberico, D.; Scott, M. E.; Lautens, M., Aryl-Aryl Bond Formation by Transition-Metal-Catalyzed Direct Axylation. Chem. Rev.2007, 107 (1),174-238. b) Chen, X.; Engle, K. M.; Wang, D.-H.; Yu, J.-Q., Palladium(II)-Catalyzed C-H Activation/C-C CrossCoupling Reactions:Versatility and Practicality. Angew. Chem., Int. Ed.2009,48 (28),5094-5115. (c) Ackermann, L. Vicente, R.; Kapdi, A. R., Transition-metal-catalyzed direct arylation of (hetero)arenes by C-H bond cleavage. Angew. Chem., Int. Ed.2009,48 (52), 9792-9826. (d) Lyons, T. W.; Sanford, M. S., Palladium-Catalyzed Ligand-Directed C-H Functionalization Reactions. Chem. Rev.2010,110 (2),1147-1169. (e) Jazzar, R. Hitce, J.; Renaudat, A., Sofack-Kreutzer, J., Baudoin, O., Functionalization of Organic Molecules by Transition-Metal-Catalyzed C(sp3)-H Activation. Chem. Eur. J. 2010,16 (9),2654-2672. (f) Yeung, C. S., Dong, V. M., Catalytic Dehydrogenative Cross-Coupling: Forming Carbon-Carbon Bonds by Oxidizing Two Carbon-Hydrogen Bonds. Chem. Rev.2011,111 (3),1251-1292. (g) Magano, J., Dunetz, J. R., Large-Scale Applications of Transition Metal-Catalyzed Couplings for the Synthesis of Pharmaceuticals. Chem. Rev.2011,111 (3),2177-2250.
2. For examples, see:(a) Daugulis, O.; Zaitsev, V. G., Anilide ortho-Arylation by Using C-H Activation Methodology. Angew. Chem., Int. Ed. 2005, 44 (26), 4046-4048. (b) Li, B.-J.; Tian, S.-L.; Fang, Z.; Shi, Z.-J., Multiple C-H Activations To Construct Biologically Active Molecules in a Process Completely Free of Organohalogen and Organometallic Components. Angew. Chem., Int. Ed.2008,47 (6), 1115-1118. (c) Wasa, M.; Engle, K. M., Yu, J.-Q., Pd(0)/PR3-Catalyzed Intermolecular Arylation of sp3 C-H Bonds. J. Am. Chem. Soc.2009,131 (29), 9886-9887. (d) Nishikata, T.; Abela, A. R.; Huang, S.; Lipshutz, B. H., Cationic palladium(II) catalysis:C-H activation/Suzuki-Miyaura couplings at room temperature. J. Am. Chem. Soc. 2010,132 (14),4978-4979. (e) Zhao, X.; Yeung, C. S.; Dong, V. M., Palladium-Catalyzed Ortho-Arylation of O-Phenylcarbamates with Simple Arenes and Sodium Persulfate. J. Am. Chem. Soc.2010,132 (16),5837-5844. (f) Wencel-Delord, J.; Nimphius, C.;Patureau, F. W.; Glorius, F., [RhⅢCp*]-Catalyzed Dehydrogenative Aryl-Aryl Bond Formation. Angew Chem., Int. Ed. 2012,51 (9), 2247-2251. (g) Peter Tsang, W. C.; Zheng, N.; Buchwald, S. L., Combined C-H Functionalization/C-N Bond Formation Route to Carbazoles. J. Am. Chem. Soc.2005, 127 (42),14560-14561. (h) Li, D.-D.; Yuan, T.-T.; Wang, G.-W., Palladium-Catalyzed ortho-Arylation of Benzamides via Direct sp2 C-H Bond Activation. J. Org. Chem. 2012,77 (7), 3341-3347. (i) Peron, F.; Fossey, C.; Cailly, T.; Fabis, F., N-Tosylcarboxamide as a Transformable Directing Group for Pd-Catalyzed C-H ortho-Arylation. Org. Lett.2012,14 (7),1827-1829.
3. (a) Colby, D. A.; Bergman, R. G.; Ellman, J. A., Stereoselective Alkylation of a, β-Unsaturated Imines via C-H Bond Activation. J. Am. Chem. Soc. 2006,128 (17), 5604-5605. (b) Colby, D. A.; Bergman, R. G.; Ellman, J. A., Synthesis of Dihydropyridines and Pyridines from Imines and Alkynes via C-H Activation. J. Am. Chem. Soc. 2008,130 (11),3645-3651. (c) Parthasarathy, K.; Jeganmohan, M. Cheng, C.-H., Rhodium-Catalyzed One-Pot Synthesis of Substituted Pyridine Derivatives from α,β-Unsaturated Ketoximes and Alkynes. Org. Lett.2008,10 (2),325-328. (d) Guimond, N.; Fagnou, K., Isoquinoline Synthesis via Rhodium-Catalyzed Oxidative Cross-Coupling/Cyclization of Aryl Aldimines and Alkynes. J. Am. Chem. Soc.2009, 131 (34),12050-12051. (e) Ding, S.; Shi, Z.; Jiao, N., Pd(Ⅱ)-Catalyzed Synthesis of Carbolines by Iminoannulation of Internal Alkynes via Direct C-H Bond Cleavage Using Dioxygen as Oxidant. Org. Lett. 2010,12 (7).1540-1543. (f) Too, P. C.; Wang, Y. F.; Chiba, S., Rhodium(Ⅲ)-Catalyzed Synthesis of Isoquinolines from Aryl Ketone O-Acyloxime Derivatives and Internal Alkynes. Org. Lett. 2010,12 (24),5688-5691. (g) Chinnagolla, R. K.; Pimparkar, S.; Jeganmohan, M., Ruthenium-Catalyzed Highly Regioselective Cyclization of Ketoximes with Alkynes by C-H Bond Activation:A Practical Route to Synthesize Substituted Isoquinolines. Org. Lett.2012,14 (12), 3032-3035. (h) Lian, Y.; Huber, T.; Hesp, K.; Bergman, R. G.; Ellman, J. A., Rhodium(III)-Catalyzed Alkenyl C-H Bond Functionalization:Convergent Synthesis of Furans and Pyrroles. Angew. Chem., Int. Ed.2013,52 (2),629-633.
4. (a) Satoh, T.; Kawamura, Y.; Miura, M.; Nomura, M., Palladium-Catalyzed Regioselective Mono- and Diarylation Reactions of 2-Phenylphenols and Naphthols with Aryl Halides. Angew. Chem., Int. Ed.1997,36 (16),1740-1742. (b) Kawamura, Y.; Satoh, T.; Miura, M.; Nomura M., Multiple Arylation of Phenols around the Oxygen under Palladium Catalysis. Chem. Lett.1999,961-962. (c) Terao, Y.; Nomoto, M.; Satoh, T.; Miura, M.; Nomura, M., Palladium-Catalyzed Dehydroarylation of Triarylmethanols and Their Coupling with Unsaturated Compounds Accompanied by C-C Bond Cleavage. J. Org. Chem.2004,69 (20),6942-6944. (d) Wakui, H.; Kawasaki, S.; Satoh, T.; Miura, M.; Nomura, M., Palladium-Catalyzed Reaction of 2-Hydroxy-2-methylpropiophenone with Aryl Bromides:A Unique Multiple Arylation via Successive C-C and C-H Bond Cleavages. J. Am. Chem. Soc.2004,126 (28),8658-8659. (e) Lu, Y.; Wang, D.-H.; Engle, K. M.; Yu, J.-Q., Pd(Ⅱ)-Catalyzed Hydroxyl-Directed C-H Olefination Enabled by Monoprotected Amino Acid Ligands. J. Am. Chem. Soc.2010,132 (16),5916-5921. (f) Lu, Y.; Leow, D.; Wang, X.; Engle, K. M.; Yu, J.-Q., Hydroxyl-directed C-H carbonylation enabled by mono-N-protected amino acid ligands:An expedient route to 1-isochromanones. Chem. Sci.2011,2, 967-971. (g) Huang, C.; Chattopadhyay, B.; Gevorgyan, V., Silanol:A Traceless Directing Group for Pd-Catalyzed o-Alkenylation of Phenols. J. Am. Chem. Soc.2011, 133 (32),12406-12409. (h) Morimoto, K.; Hirano, K.; Satoh, T.; Miura, M., Synthesis of Isochromene and Related Derivatives by Rhodium-Catalyzed Oxidative Coupling of Benzyl and Allyl Alcohols with Alkynes. J. Org. Chem.2011,76 (22),9548-9551.
5. (a) Garcia-Rubia, A.; Arrayas, R. G.; Carretero, J. C., Palladium(II)-Catalyzed Regioselective Direct C2 Alkenylation of Indoles and Pyrroles Assisted by the N-(2-Pyridyl)sulfonyl Protecting Group. Angew. Chem. Int. Ed.2009,48 (35), 6511-6515. (b) Garcia-Rubia, A.; Urones, B.; Arrayas, R. G.; Carretero, J. C. PdⅡ-Catalyzed C-H Olefination of N-(2-Pyridyl)sulfonyl Anilines and Arylalkylamines. Angew. Chem. Int. Ed.2011, 50 (46),10927-10931. (c) Garcia-Rubia, A.; Fernandez-Ibanez, M. A.; Arrayas, R. G.; Carretero, J. C.,2-Pyridyl Sulfoxide:A Versatile and Removable Directing Group for the PdⅡ-Catalyzed Direct C-H Olefination of Arenes. Chem. Eur. J.2011,17 (13),3567-3570. (d) Yu, M.; Liang, Z.; Wang, Y.; Zhang, Y, Palladium(Ⅱ)-Catalyzed Direct Alkenylation and Arylation of Arenes:Removable 2-Pyridylsulfinyl Group Assisted C-H Bond Activation. J. Org. Chem.2011,76 (12),4987-4994. (e) Romero-Revilla, J. A.; Garcia-Rubia, A.; Arrayas R. G.; Fernandez-Ibanez, M. A.; Carretero, J. C., Palladium-catalyzed coupling of arene C-H bonds with methyl- and arylboron reagents assisted by the removable 2-pyridylsulfinyl group. J. Org. Chem.2011,76 (22),9525-9530. (f) Zhang, X.; Yu, M.; Yao, J.; Zhang, Y., Palladium-Catalyzed Regioselective Arylation of Arene C-H Bond Assisted by the Removable 2-Pyridylsulfinyl Group. Synlett 2012, 23,463-467.
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