Practical Aspects and Mechanism of Asymmetric Hydrogenation with Chiral Half-Sandwich Complexes

Václavík, Jiří; Šot, Petr; Vilhanová, Beáta; Pecháček, Jan; Kuzma, Marek; Kačer, Petr

doi:10.3390/molecules18066804

Cited by 50 publications

(37 citation statements)

References 88 publications

(141 reference statements)

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“…The objective of this review is not to recount the early history of the transfer hydrogenation of C=N bonds, including asymmetric versions, because this has been reported adequately in a range of other reviews. [1][2][3][4][5][6][7][8][9][10][11][12][13][14] In addition, the mechanisms of the reactions have been discussed in detail. Hence whilst some recap is valuable in order to set the newer results into appropriate context, this review will focus primarily, although not exclusively, on newer developments in this area reported in the last 10 years, i.e.…”

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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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confidence: 99%

Imino Transfer Hydrogenation Reductions

Wills

2016

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“…More profound modifications of N-R-sulfonyl fragment have been showed, aiming at substantial changes in catalyst's properties, e. g., for immobilization, or for conducting ATH in different media (water, ionic liquid, etc.) [17]. It is evident that the literature contains many interesting examples of structural variations.…”

Section: Modification Of the Sulfonyl Moietymentioning

confidence: 99%

Asymmetric Transfer Hydrogenation of C=O and C=N Bonds Catalyzed by [Ru(η6 arene)(diamine)] Complexes: A Multilateral Study

Matuška¹,

Kindl²,

Kačer³

2017

New Advances in Hydrogenation Processes - Fundamentals and Applications

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In these days, asymmetric transfer hydrogenation (ATH) is a very attractive method for synthesis of enantioenriched chiral compounds, especially fine chemicals such as drugs or agrochemicals. In this review, several topics related to the asymmetric transfer hydrogenation of ketones and cyclic or acyclic imines are discussed. Initially, the reaction mechanism of the ATH of ketones and imines, mainly 3,4-dihydroisoquinoline derivates, is examined. Next, typical reaction conditions, structural effects of the catalyst and a substrate, and analytical methods used for ATH monitoring and practical applications of the ATH in the chemical industry are described.

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“…Among those methods, catalytic asymmetric transfer hydrogenation (ATH) of ketones and imines, pioneered by Noyori et al, [1] is now very well established. [2][3][4][5][6][7][8][9][10] Still, this catalytic system has certain limitations, such as the poor reactivity of 1-aryl-3,4-dihydroisoquinolines (1-Ar-DHIQs) as precursors of the chiral 1aryl-1,2,3,4-tetrahydroisoquinoline (1-Ar-THIQ) motif present in naturally-occurring alkaloids (Cryptostylines) and drugs (e.g., Solifenacin [11] or Gantacurium [12] ). Efficient asymmetric hydrogenation protocols for 1-Ar-DHIQs have been reported anhydrous phosphoric acid as an inexpensive additive.…”

Section: Introductionmentioning

confidence: 99%

Asymmetric Transfer Hydrogenation of 1‐Aryl‐3,4‐Dihydroisoquinolines Using a Cp*Ir(TsDPEN) Complex

et al. 2017

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We report herein a simple alternative method for the asymmetric transfer hydrogenation (ATH) of 1‐aryl‐3,4‐dihydroisoquinolines (1‐Ar‐DHIQs) that are known to be challenging substrates owing to their poor reactivity. The hydrogenation protocol employs the readily available Cp*Ir(TsDPEN) {where Cp* = pentamethylcyclopentadienyl and TsDPEN = (S,S)‐HNCHPhCHPhNTs2–} catalytic complex, 2‐propanol and HCOOH/triethylamine mixture as the solvent and hydrogen donor, and anhydrous phosphoric acid as an inexpensive additive. The series of examined substrates shows a favorable tolerance to various functional groups. Unlike 1‐alkyl‐DHIQs, where the enantiomeric excess (ee) starkly changes during the course of hydrogenation, 1‐Ar‐DHIQs exhibit a constant ee value, which makes the method practical and useful for the production of fine chemicals containing the 1,2,3,4‐tetrahydroisoquinoline motif.

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Practical Aspects and Mechanism of Asymmetric Hydrogenation with Chiral Half-Sandwich Complexes

Cited by 50 publications

References 88 publications

Imino Transfer Hydrogenation Reductions

Imino Transfer Hydrogenation Reductions

Asymmetric Transfer Hydrogenation of C=O and C=N Bonds Catalyzed by [Ru(η6 arene)(diamine)] Complexes: A Multilateral Study

Asymmetric Transfer Hydrogenation of 1‐Aryl‐3,4‐Dihydroisoquinolines Using a Cp*Ir(TsDPEN) Complex

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