Ru-Catalyzed Asymmetric Transfer Hydrogenation of α-Trifluoromethylimines

Wu, Meng; Cheng, Tanyu; Ji, Min; Liu, Guohua

doi:10.1021/acs.joc.5b00177

Cited by 51 publications

(26 citation statements)

References 70 publications

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“…However, further single crystal X-ray crystallographic study confirmed that instead of the chloride counterion, the anion that was really forming the salt was hexafluorophosphate . This fact was also corroborated by 31 P NMR experiment where a septet (J = 714.4 Hz) was identified at δ = -69.15, while in the 19 F NMR experiment, the magnetic equivalence of the six fluorines in the [PF 6 ]anion gave a doublet with a J = 714. 4 Hz at δ = -71.41 (see Figures SI26 and SI27, Supporting Information).…”

Section: Figure 1 Representative Natural Systems Prepared Through Thesupporting

confidence: 53%

Unexpected PF6 Anion Metathesis during the Bischler–Napieralski Reaction: Synthesis of 3,4-Dihydroisoquinoline Hexafluorophosphates and Their Tetrahydroisoquinoline Related Alkaloids

2019

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A series of N-phenethylcinnamamides were subjected to the Bischler–Napieralski reaction to furnish diverse 1-styryl-3,4-dihydroisoquinolines. We noticed that the desired products were unstable when the reaction was performed under conventional solvent conditions. However, when [bmim]PF6 was used as the reaction media, the nature of the Bischler–Napieralski reaction promoted an unusual in situ ionic interchange between this ionic liquid and the dihydroisoquinoline core that led to the stabilization of the desired 1-styryl-3,4-dihydroisoquinolines, allowing their isolation as hexafluorophosphate salts. Finally, the one-pot reduction/reductive methylation process afforded the N-methyl derivatives, establishing that our findings can be an efficient and useful strategy for the concise synthesis of tetrahydroisoquinoline alkaloids.

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Section: Figure 1 Representative Natural Systems Prepared Through Thesupporting

confidence: 53%

Unexpected PF6 Anion Metathesis during the Bischler–Napieralski Reaction: Synthesis of 3,4-Dihydroisoquinoline Hexafluorophosphates and Their Tetrahydroisoquinoline Related Alkaloids

2019

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“…[88] Ru(II)-catalysed ATH of α-trifluoromethylimines was also achieved using TsDPEN-based catalysts under aqueous conditions ( Figure 20). [89] Several reports have recently appeared describing the ATH reduction of cyclic sulfamidates and sulfamides, following the report of this in 2010. [90] The synthetic routes to key substrates and their reductions by Rh(III) catalysts are shown in Figure 21.…”

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confidence: 99%

Imino Transfer Hydrogenation Reductions

Wills

2016

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This review contains a summary of recent developments in the transfer hydrogenation of C=N bonds, with a particularly focus on reports from within the last 10 years and asymmetric transformations. However, earlier work in the area is also discussed in order to provide context for the more recent results described. I focus strongly on the Ru/TsDPEN class of asymmetric transfer hydrogenation reactions originally reported by Noyori et al., together with examples of their applications, particularly to medically valuable target molecules. The recent developments in the area of highly active imine-reduction catalysts, notably those based on iridium, are also described in some detail. I discuss diastereoselective reduction methods as a route to the synthesis of chiral amines using transfer hydrogenation. The recent development of a methodology for positioning reduction complexes within chiral proteins, permitting the generation of asymmetric reduction products through a directed modification of the protein environment in a controlled manner, is also discussed.

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“…IR (film, NaCl): 3369, 2955, 1712, 1514, 1449, 1435, 1292, 1241, 1201, 1175, 1124, 1082: m/z calcd for C 17 H 17 F 3 6, 153.6, 139.2, 137.8, 135.2, 132.6, 129.4, 129.3, 127.9, 125.0 (q, J(C−F) = 282 Hz), 115.9, 115.0, 61.6 (q, J(C−F) = 30 Hz), 55.8, 26.8. 19 F NMR (CDCl 3 ): −74.1 (d,J = 7.2 Hz). IR (film, NaCl): 3362, 2933, 1720, 1683, 1514, 1464, 1359, 1236, 1169, 1124, 1036 3383, 2837, 1615, 1594, 1511, 1489, 1450, 1232, 1179, 1148, 1118, 1034: m/z calcd for C 15 H 14 F 4 (S)-4-Methoxy-N-(2,2,2-trifluoro-1-(3-methoxyphenyl)ethyl)-aniline (2y).…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Palladium(II)-Catalyzed Enantioselective Synthesis of α-(Trifluoromethyl)arylmethylamines

2016

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We describe a method for the synthesis of α-(trifluoromethyl)arylmethylamines that consists of the palladium(II)-catalyzed addition of arylboroxines to imines derived from trifluoroacetaldehyde. Palladium acetate is used as a catalyst with electron-neutral or electron-rich arylboroxines, and it was found that addition of an ammonium or silver salt was crucial to promote the reaction of electron-poor boroxines. With (S)-t-Bu-PyOX as the chiral ligand, this method delivers a variety of α-trifluoromethylated amines in 57-91% yield and with greater than 92% ee in most cases.

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Ru-Catalyzed Asymmetric Transfer Hydrogenation of α-Trifluoromethylimines

Cited by 51 publications

References 70 publications

Unexpected PF6 Anion Metathesis during the Bischler–Napieralski Reaction: Synthesis of 3,4-Dihydroisoquinoline Hexafluorophosphates and Their Tetrahydroisoquinoline Related Alkaloids

Unexpected PF6 Anion Metathesis during the Bischler–Napieralski Reaction: Synthesis of 3,4-Dihydroisoquinoline Hexafluorophosphates and Their Tetrahydroisoquinoline Related Alkaloids

Imino Transfer Hydrogenation Reductions

Palladium(II)-Catalyzed Enantioselective Synthesis of α-(Trifluoromethyl)arylmethylamines

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