Asymmetric Aerobic Oxidative Cross-Coupling of Tetrahydroisoquinolines with Alkynes

Huang, Tianyu; Liu, Xiaohua; Lang, Jiawen; Xu, Jian; Lin, Lili; Feng, Xiaoming

doi:10.1021/acscatal.7b01912

Cited by 71 publications

(21 citation statements)

References 81 publications

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“…In comparison, an enantioselective Sonogashira-type cross-dehydrogenative coupling (CDC) of C( sp 3 )−H bonds with low-cost terminal alkynes would be more ideal due to the ready availability of both coupling partners. In this respect, Li and others have pioneered in establishing enantioselective alkynylation of C( sp 3 )−H bonds adjacent to nitrogen with terminal alkynes 23–32 . The stereochemical control was elegantly implemented via chiral Lewis acid-catalyzed nucleophilic addition to the in situ generated iminium ions (Fig.…”

Section: Introductionmentioning

confidence: 99%

Copper-catalyzed enantioselective Sonogashira-type oxidative cross-coupling of unactivated C(sp3)−H bonds with alkynes

et al. 2019

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Transition metal-catalyzed enantioselective Sonogashira-type oxidative C(sp3)—C(sp) coupling of unactivated C(sp3)−H bonds with terminal alkynes has remained a prominent challenge. The difficulties mainly stem from the regiocontrol in unactivated C(sp3)—H bond functionalization and the inhibition of readily occurring Glaser homocoupling of terminal alkynes. Here, we report a copper/chiral cinchona alkaloid-based N,N,P-ligand catalyst for asymmetric oxidative cross-coupling of unactivated C(sp3)—H bonds with terminal alkynes in a highly regio-, chemo-, and enantioselective manner. The use of N-fluoroamide as a mild oxidant is essential to site-selectively generate alkyl radical species while efficiently avoiding Glaser homocoupling. This reaction accommodates a range of (hetero)aryl and alkyl alkynes; (hetero)benzylic and propargylic C(sp3)−H bonds are all applicable. This process allows expedient access to chiral alkynyl amides/aldehydes. More importantly, it also provides a versatile tool for the construction of chiral C(sp3)—C(sp), C(sp3)—C(sp2), and C(sp3)—C(sp3) bonds when allied with follow-up transformations.

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Section: Introductionmentioning

confidence: 99%

Copper-catalyzed enantioselective Sonogashira-type oxidative cross-coupling of unactivated C(sp3)−H bonds with alkynes

et al. 2019

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“…In 2017, the asymmetric aerobic oxidative cross-coupling of tetrahydroisoquinolines with alkynes was reported by Feng and Liu on the basis of a chiral N,N 0 -dioxide ligand 113/zinc(II)/iron (II) bimetallic cooperative catalytic system [85]. As shown in Scheme 46, this catalyst system proved to be efficient for the formation of various chiral a-alkynyl substituted tetrahydroisoquinolines 114 starting from the corresponding tetrahydroisoquinolines 115 and alkynes 116.…”

Section: Enantioselective Cross-coupling Reactionsmentioning

confidence: 98%

“…In addition, White and Shaw reported the use of 7.5 mol% of chiral salen iron complex 130 in chloroform at 50°C to promote the asymmetric Conia-ene carbocyclization of a range of alkynyl ketones 131 bearing an electron-withdrawing a-substituent (R 2 ) Scheme 46. Oxidative cross-coupling of tetrahydroisoquinolines with alkynes [85].…”

Section: Enantioselective Cyclizationsmentioning

confidence: 99%

Recent developments in enantioselective iron-catalyzed transformations

Pellissier

2019

Coordination Chemistry Reviews

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Scheme 2. Chiral iron catalysts described by Morris, Gao and Mezzetti groups [13,14,16]. Scheme 3. Transfer hydrogenation of alkyl aryl ketones catalyzed by chiral (NH) 2 P 2 macrocyclic iron complexes [17]. Scheme 4. Transfer hydrogenation of alkyl aryl ketones and a phosphinyl imine catalyzed by chiral (NH) 2 P 2 macrocyclic iron complexes [18]. Scheme 5. Transfer hydrogenation of benzyls without base additive [19]. Scheme 8. Hydrogenation of alkyl aryl ketones catalyzed by an iron catalyst derived from a chiral PNP' ligand [29]. Scheme 9. Hydrogenation of alkyl aryl ketones catalyzed by an iron catalyst derived from a chiral monohydride unsymmetrical PNHP' pincer ligand [30]. Scheme 10. Hydrogenation of ketones catalyzed by a chiral cyclopentadienone iron tricarbonyl complex [31]. Scheme 11. Hydrogenation of para-methoxyacetophenone catalyzed by a chiral cyclopentadienone iron tricarbonyl complex embedded in streptavidin [32]. Scheme 14. Hydrosilylation of alkyl aryl ketones catalyzed by a chiral iminopyridine-oxazoline iron complex [41]. Scheme 15. Hydrosilylation of para-phenyl acetophenone catalyzed by a chiral bis(oxazolinyl)phenyl iron complex [42]. Scheme 58. Synthesis of esomeprazole through sulfoxidation [104]. Scheme 59. CAH Alkylation of indoles with aromatic alkenes [105].

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“…Recently, Feng et al introduced a chiral N,N'-oxide ligand, together with a Zn(II)-Fe(II) bimetallic cooperative catalytic system, for the asymmetric alkynylation of N-PMPsubstituted THIQs under a molecular oxygen atmosphere and mild conditions [50]. The presence of both, 5 Å molecular sieves NaB[3,5-(F3C)2C6H3]4 was found to be crucial to attain higher yields and e.e.'s.…”

Section: Scheme 34mentioning

confidence: 99%

Synthesis of Propargylamines by Cross-Dehydrogenative Coupling

Alonso

Bosque

Chinchílla

et al. 2019

CGC

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Propargylamines are versatile compounds for heterocyclic synthesis, some of which are current drugs prescribed to treat patients with Parkinson’s disease. There are different methods to synthesize propargylamines, however, modern chemistry has moved progressively to rely on new strategies that meet the principles of Green Chemistry. In this context, propargylamines are readily accessible by the cross-dehydrogenative coupling (CDC) of two C-H bonds (i.e., NCsp3-H and Csp-H bonds); surely, CDC can be considered the most atom-economic and efficient manner to form C-C bonds. The aim of this review is to provide a comprehensive survey on the synthesis of propargylamines by the CDC of amines and terminal alkynes from three fronts: (a) transition-metal homogeneous catalysis, (b) transition-metal heterogeneous catalysis and (c) photoredox catalysis. A section dealing with the asymmetric synthesis of chiral propargylamines is also included. Special attention is also devoted to the proposed reaction mechanisms.

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Asymmetric Aerobic Oxidative Cross-Coupling of Tetrahydroisoquinolines with Alkynes

Cited by 71 publications

References 81 publications

Copper-catalyzed enantioselective Sonogashira-type oxidative cross-coupling of unactivated C(sp3)−H bonds with alkynes

Copper-catalyzed enantioselective Sonogashira-type oxidative cross-coupling of unactivated C(sp3)−H bonds with alkynes

Recent developments in enantioselective iron-catalyzed transformations

Synthesis of Propargylamines by Cross-Dehydrogenative Coupling

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