- Electrocatalytic C(sp3)-H/C(sp)-H cross-coupling in continuous flow through TEMPO/copper relay catalysis
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Electrocatalytic dehydrogenative C(sp3)-H/C(sp)-H cross-coupling of tetrahydroisoquinolines with terminal alkynes has been achieved in a continuous-flow microreactor through 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO)/copper relay catalysis. The reaction
- Guo, Bin,Xu, Hai-Chao
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supporting information
p. 2650 - 2656
(2021/11/30)
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- An oxidant- And catalyst-free electrooxidative cross-coupling approach to 3-tetrahydroisoquinoline substituted coumarins
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A direct electrooxidative cross-dehydrogenative-coupling (CDC) reaction betweenN-aryl-tetrahydroisoquinolines and 4-hydroxycoumarins has been realized. This protocol provides a green, mild and fast method to construct 3-tetrahydroisoquinoline substituted coumarins in the absence of any catalysts and exogenous oxidants. A variety ofN-aryl-tetrahydroisoquinolines and 4-hydroxycoumarins are compatible with this transformation to give the corresponding products in moderate to excellent yields. Moreover, the results of control experiments, cyclic voltammetry experiments, and density functional theory (DFT) calculations indicated that the electrooxidative CDC reaction might involve both radical addition and nucleophilic addition processes.
- Kong, Yanyan,Kim, Jung Keun,Li, Yabo,Zhang, Jianye,Huang, Mengmeng,Wu, Yangjie
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supporting information
p. 1274 - 1279
(2021/02/26)
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- Visible-light induced Cross-Dehydrogenative-Coupling (CDC) reactions of N-aryl tetrahydroisoquinolines under aerobic conditions
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A visible-light induced cross-dehydrogenative-coupling (CDC) reaction of N-aryl tetrahydroisoquinolines was developed under mild aerobic conditions. This protocol proceeded smoothly with a large range of nucleophiles (nitroalkane, dimethyl phosphite, dimethyl malonate, N-methyl indole, TMSCN) under metal-free conditions and an oxygen atmosphere, forming a new C–C bond. Visible-light played a significant acceleration effect in this reaction.
- Lin, Chao,Li, Peiwu,Wang, Lin
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supporting information
(2021/05/19)
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- Photoredox/cobaloxime co-catalyzed allylation of amines and sulfonyl hydrazines with olefins to access α-allylic amines and allylic sulfones
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Herein, we reported a dual-catalytic platform for the allylation of amines and sulfonyl hydrazines with olefins to selectively access α-allylic amines and allylic sulfones in good yields by combining photoredox catalysis and cobaloxime catalysis. This strategy avoided the use of a stoichiometric amount of terminal oxidant and the use of pre-functionalized allylic precursors, representing a green and ideal atom- & step-economical process. Good substrate scope and gram-scale synthesis demonstrated the utility of this protocol. Mechanistic studies revealed that a radical process is probably involved in this reaction.
- Tong, Qing-Xiao,Xu, Hui,Zhang, Hong,Zhong, Jian-Ji
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supporting information
p. 8227 - 8231
(2021/10/12)
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- CuII/TEMPO-Catalyzed Enantioselective C(sp3)–H Alkynylation of Tertiary Cyclic Amines through Shono-Type Oxidation
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A novel strategy for asymmetric Shono-type oxidative cross-coupling has been developed by merging copper catalysis and electrochemistry, affording C1-alkynylated tetrahydroisoquinolines with good to excellent enantioselectivity. The use of TEMPO as a co-catalytic redox mediator is crucial not only for oxidizing a tetrahydroisoquinoline to an iminium ion species but also for decreasing the oxidation potential of the reaction. A novel bisoxazoline ligand is also reported.
- Chen, Zhi-Hao,Gao, Pei-Sen,Mei, Tian-Sheng,Sun, Bing,Wang, Zhen-Hua,Weng, Xin-Jun,You, Shu-Li,Zheng, Chao
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supporting information
p. 15254 - 15259
(2020/06/23)
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- Electrochemical Cross-Dehydrogenative Coupling of N-Aryl-tetrahydroisoquinolines with Phosphites and Indole
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A metal- and reagent-free, electrochemical cross-dehydrogenative coupling reaction of N-aryl-tetrahydroisoquinolines with phosphites and indole is developed. This method provides an environmentally benign and simple approach for the construction of C–P an
- Xie, Wenxia,Liu, Nian,Gong, Bowen,Ning, Shulin,Che, Xin,Cui, Lili,Xiang, Jinbao
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p. 2498 - 2501
(2019/04/01)
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- Aerobic α-Oxidation of N-Substituted Tetrahydroisoquinolines to Dihydroisoquinolones via Organo-photocatalysis
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An efficient visible-light-induced α-oxidation of N-substituted tetrahydroisoquinolines to dihydroisoquinolones has been developed using eosin Y as an organo-photocatalyst and oxygen as a green oxidant. The reactions were carried out under mild reaction conditions; the desired dihydroisoquinolones were obtained in up to 96% yield at room temperature under oxygen atmosphere. This transformation provides a convenient route to dihydroisoquinolones with a wide range of substrates. (Figure presented.).
- Aganda, Kim Christopher C.,Hong, Boseok,Lee, Anna
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supporting information
p. 1124 - 1129
(2019/01/25)
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- Iminium Ion and N-Hydroxyimide as the Surrogate Components in DEAD-Promoted Oxidative Ugi Variant
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A practical metal-free oxidative Ugi-type three-component assembly has been achieved efficiently, employing a tertiary-amine-derived iminium ion as an imine surrogate, N-hydroxyimide as an acid surrogate, and DEAD as an oxidant. This dual-surrogate Ugi variant proceeded with a broad substrate scope and desired functional group tolerance, leading to a wide range of N-alkyl-N-acyl aminophthalimide and N-alkyl-N-acylaminosuccinimide derivatives in good isolated yields.
- Wang, Jiankun,Sun, Yilin,Jiang, Mu-Han,Hu, Tian-Yu,Zhao, Yong-Jie,Li, Xin,Wang, Guangji,Hao, Kun,Zhen, Le
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p. 13121 - 13131
(2018/11/20)
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- Reactions Catalysed by a Binuclear Copper Complex: Relay Aerobic Oxidation of N-Aryl Tetrahydroisoquinolines to Dihydroisoquinolones with a Vitamin B1 Analogue
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N-Aryl tetrahydroisoquinolines were oxidised to dihydroisoquinolones through the relay catalysis of a binuclear paddle-wheel copper complex and a vitamin B1 analogue with oxygen as oxidant. Mechanistic studies revealed that the copper catalyst oxidises amines to the corresponding iminium salts, which are then oxygenated to lactam products by catalysis of the vitamin B1 analogue.
- Liu, Yuxia,Wang, Chao,Xue, Dong,Xiao, Miao,Liu, Jiao,Li, Chaoqun,Xiao, Jianliang
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supporting information
p. 3062 - 3066
(2017/03/13)
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- DEAD-Promoted Oxidative Ugi-Type Reaction Including an Unprecedented Ugi Amidation Assisted by Dicarboxylic Acids
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A mild and metal-free DEAD-promoted (DEAD = diethyl azodicarboxylate) oxidative Ugi-type reaction of tertiary amines has been demonstrated. The reaction gives easy access to α-amino amides and imides with diverse functional groups in good isolated yields. This Ugi-type approach achieves an unprecedented synthesis of α-amino amide analogues with the assistance of dicarboxylic acids, and not water, for the introduction of the carbonyl oxygen atom of the amide moiety. Mechanistic studies indicated that the dicarboxylic acids may readily undergo an intramolecular annulation, instead of the Mumm rearrangement, to give the desired amide with one molecule of anhydride released.
- Wang, Jiankun,Sun, Yilin,Wang, Guangji,Zhen, Le
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supporting information
p. 6338 - 6348
(2017/11/21)
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- Bifunctional organic sponge photocatalyst for efficient cross-dehydrogenative coupling of tertiary amines to ketones
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A novel bifunctional organic sponge photocatalyst can enable the efficient coupling of tertiary amines with ketones in water. The asymmetric transformation can be also achieved by using this sponge photocatalyst.
- Zhang, Teng,Liang, Weiwei,Huang, Yuxing,Li, Xingrong,Liu, Yizhen,Yang, Bo,He, Chuanxin,Zhou, Xuechang,Zhang, Junmin
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supporting information
p. 12536 - 12539
(2017/11/30)
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- Copper-catalyzed asymmetric sp3 C-H arylation of tetrahydroisoquinoline mediated by a visible light photoredox catalyst
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This report describes a highly enantioselective oxidative sp3 C-H arylation of N-aryltetrahydroisoquinolines (THIQs) through a dual catalysis platform. The combination of the photoredox catalyst, [Ir(ppy)2(dtbbpy)]PF6, and chiral copper catalysts provide a mild and highly effective sp3 C-H asymmetric arylation of THIQs.
- Querard, Pierre,Perepichka, Inna,Zysman-Colman, Eli,Li, Chao-Jun
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supporting information
p. 2636 - 2643
(2017/01/09)
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- Rapid Microwave-Assisted Synthesis of N-Aryl 1,2,3,4-Tetrahydroisoquinolines
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N-aryl 1,2,3,4-tetrahydroisoquinolines were prepared rapidly in good yields by the microwave-assisted Pd-catalysed coupling of (hetero)aryl iodides or bromides with 1,2,3,4-tetrahydroisoquinoline. Reactions were typically complete within 5 min for aryl iodides and within 30 min for pyridyl bromides.
- Forni, José Augusto,Brzozowski, Martin,Tsanaktsidis, John,Savage, G. Paul,Polyzos, Anastasios
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p. 1890 - 1893
(2015/12/26)
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- Efficient merging of copper and photoredox catalysis for the asymmetric cross-dehydrogenative-coupling of alkynes and tetrahydroisoquinolines
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A highly efficient catalytic asymmetric alkynylation of prochiral CH2 groups in tetrahydroisoquinoline was developed using copper catalyzed cross-dehydrogenative-coupling of sp3 and sp C-H bonds with the assistance of a photocatalyst and visible light.
- Perepichka, Inna,Kundu, Soumen,Hearne, Zo,Li, Chao-Jun
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supporting information
p. 447 - 451
(2015/02/05)
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- Cross-coupling hydrogen evolution reaction in homogeneous solution without noble metals
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A highly efficient noble-metal-free homogeneous system for a cross-coupling hydrogen evolution (CCHE) reaction is developed. With cheap, earth-abundant eosin Y and molecular catalyst Co(dmgH)2Cl2, good to excellent yields for coupling reactions with a variety of isoquinolines and indole substrates and H2 have been achieved without any sacrificial oxidants. Mechanistic insights provide rich information on the effective, clean, and economic CCHE reaction.
- Zhong, Jian-Ji,Meng, Qing-Yuan,Liu, Bin,Li, Xu-Bing,Gao, Xue-Wang,Lei, Tao,Wu, Cheng-Juan,Li, Zhi-Jun,Tung, Chen-Ho,Wu, Li-Zhu
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supporting information
p. 1988 - 1991
(2014/05/06)
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- A Cascade Cross-Coupling and in Situ Hydrogenation Reaction by Visible Light Catalysis
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An elegant cascade cross-coupling and in situ hydrogenation reaction has been established by visible light catalysis. Combining cheap and earth-abundant eosin Y as a photosensitizer and the cobalt chloride complex, Co(dmgH)2Cl2 (dmgH=dimethylglyoximate), as a catalyst, the desired oxidative cross-coupling products and reductive hydrogenation products could be achieved in good to excellent yields without use of any external oxidants and reductants under visible light irradiation.
- Zhong, Jian-Ji,Wu, Cheng-Juan,Meng, Qing-Yuan,Gao, Xue-Wang,Lei, Tao,Tung, Chen-Ho,Wu, Li-Zhu
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supporting information
p. 2846 - 2852
(2016/02/19)
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- Molecular iodine catalyzed cross-dehydrogenative coupling reaction between two sp3 C-H bonds using hydrogen peroxide
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A useful method for molecular iodine catalyzed oxidative C-C bond formation between tertiary amines and a carbon nucleophile using hydrogen peroxide as the terminal oxidant is reported. This is the first report of a molecular iodine catalyzed cross-dehydrogenative coupling (CDC) reaction between two sp 3 C-H bonds.
- Nobuta, Tomoya,Tada, Norihiro,Fujiya, Akitoshi,Kariya, Atsumasa,Miura, Tsuyoshi,Itoh, Akichika
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supporting information
p. 574 - 577
(2013/04/10)
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- Eosin y catalyzed visible light oxidative C-C and C-P bond formation
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Eosin Y catalyzes efficiently the visible light mediated coupling of sp3 C-H bonds adjacent to the nitrogen atom in tetrahydroisoquinoline derivatives in the absence of an external oxidant. Nitroalkanes, dialkyl malonates, malononitrile, and di
- Hari, Durga Prasad,Koenig, Burkhard
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supporting information; experimental part
p. 3852 - 3855
(2011/09/19)
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- Platinum-catalyzed cross-dehydrogenative coupling reaction in the absence of oxidant
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A third strategy for cross-dehydrogenative coupling reaction has been reported via platinum-catalyzed sp3 C-H and sp3 C-H coupling reaction in the absence of oxidant. Nitroalkanes as well as dialkyl malonate derivatives, β-keto esters and malononitrile are active participants in this coupling reaction. Both cyclic and acyclic non-activated simple ketones are good reactants in this reaction.
- Shu, Xing-Zhong,Yang, Yan-Fang,Xia, Xiao-Feng,Ji, Ke-Gong,Liu, Xue-Yuan,Liang, Yong-Min
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supporting information; experimental part
p. 4077 - 4079
(2010/10/21)
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- Selective functionalization of sp3 C - H bonds adjacent to nitrogen using (diacetoxyiodo)benzene (DIB)
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(Chemical Equation Presented) A PhI(OAc)2 mediated selective functionalization of sp3C - H bonds adjacent to a nitrogen atom has been reported. When piperidine derivates were used, direct diacetoxylation of α and β sp3 C - H adjacent to a nitrogen atom were observed to afford various cis-2,3-diacetoxylated piperidines. On the other hand, tetrahydroisoquinoline derivatives gave various α-C - H functionalized products in the presence of PhI(OAc)2. Nitroalkanes, dialkyl malonates, and β-keto ester are active participants in this coupling reaction. Meanwhile, α-amino nitriles can also be obtained by oxidative coupling of amineswithmalononitrile. 2009 American Chemical Society.
- Shu, Xing-Zhong,Xia, Xiao-Feng,Yang, Yan-Fang,Ji, Ke-Gong,Liu, Xue-Yuan,Liang, Yong-Min
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supporting information; experimental part
p. 7464 - 7469
(2010/01/06)
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- Studies on Cu-catalyzed asymmetric alkynylation of tetrahydroisoquinoline derivatives
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Enantioselective C-C bond formations between the sp3 C-H bond of prochiral CH2 and terminal alkynes via the cross-dehydrogenative coupling (CDC) reaction were studied. Efficient asymmetric syntheses of alkynyl tetrahydroisoquinoline derivatives were achieved by using a catalytic amount of CuOTf together with PyBox chiral ligand. When dihydroisoquinolinium salts were used as electrophiles, the combination of CuBr/QUINAP provided the best results for asymmetric syntheses of alkynyl tetrahydroisoquinoline derivatives. The factors influencing the enantioselectivity were studied.
- Li, Zhiping,MacLeod, Patricia D.,Li, Chao-Jun
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p. 590 - 597
(2007/10/03)
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