Highly Efficient Iridium Catalyst for Asymmetric Transfer Hydrogenation of Aromatic Ketones under Base-Free Conditions

Dong, Zhen‐Rong; Li, Yanyun; Chen, Jianshan; Li, Baozhu; Xing, Yan; Gao, Jingxiang

doi:10.1021/ol047412n

Cited by 126 publications

(32 citation statements)

References 23 publications

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“…2-Nitrobenzyl alkylated HOMedU products 3a–3e were obtained when 2 was heated neat with their corresponding 2-nitrobenzyl alcohols. 2-Nitrobenzyl alcohol is commercially available, and the synthesis of the racemic α-methyl-2-nitrobenzyl alcohol has been reported (31). Racemic α-isopropyl- and α- tert -butyl-2-nitrobenzyl alcohols were synthesized using a Grignard reaction with 2-nitrophenyl-magnesium chloride (generated in situ from 1-iodo-2-nitrobenzene and phenylmagnesium chloride) and isobutyraldehyde or trimethylacetaldehyde, respectively (Scheme 2).…”

Section: Resultsmentioning

confidence: 99%

Improved nucleotide selectivity and termination of 3′-OH unblocked reversible terminators by molecular tuning of 2-nitrobenzyl alkylated HOMedU triphosphates

Litosh

Stupi

et al. 2011

Nucleic Acids Research

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We describe a novel 3′-OH unblocked reversible terminator with the potential to improve accuracy and read-lengths in next-generation sequencing (NGS) technologies. This terminator is based on 5-hydroxymethyl-2′-deoxyuridine triphosphate (HOMedUTP), a hypermodified nucleotide found naturally in the genomes of numerous bacteriophages and lower eukaryotes. A series of 5-(2-nitrobenzyloxy)methyl-dUTP analogs (dU.I–dU.V) were synthesized based on our previous work with photochemically cleavable terminators. These 2-nitrobenzyl alkylated HOMedUTP analogs were characterized with respect to incorporation, single-base termination, nucleotide selectivity and photochemical cleavage properties. Substitution at the α-methylene carbon of 2-nitrobenzyl with alkyl groups of increasing size was discovered as a key structural feature that provided for the molecular tuning of enzymatic properties such as single-base termination and improved nucleotide selectivity over that of natural nucleotides. 5-[(S)-α-tert-Butyl-2-nitrobenzyloxy]methyl-dUTP (dU.V) was identified as an efficient reversible terminator, whereby, sequencing feasibility was demonstrated in a cyclic reversible termination (CRT) experiment using a homopolymer repeat of ten complementary template bases without detectable UV damage during photochemical cleavage steps. These results validate our overall strategy of creating 3′-OH unblocked reversible terminator reagents that, upon photochemical cleavage, transform back into a natural state. Modified nucleotides based on 5-hydroxymethyl-pyrimidines and 7-deaza-7-hydroxymethyl-purines lay the foundation for development of a complete set of four reversible terminators for application in NGS technologies.

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Section: Resultsmentioning

confidence: 99%

Improved nucleotide selectivity and termination of 3′-OH unblocked reversible terminators by molecular tuning of 2-nitrobenzyl alkylated HOMedU triphosphates

Litosh

Stupi

et al. 2011

Nucleic Acids Research

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“…They also theoretically investigated the mechanism for asymmetric transfer hydrogenation in 2001 [8]. Other transition metal catalysts containing tetradentate diaminodiphosphine or aminodiphosphine ligands have also been shown to be very effective for transfer hydrogenation of ketones [12][13][14][15]. AbdurRashid and Morris have developed many ruthenium complexes used as hydrogen catalysts [16,17] and clarified the reaction mechanisms [18].…”

Section: Introductionmentioning

confidence: 99%

Theoretical investigation on the mechanisms of transfer hydrogenation of ketones catalyzed by iridium complexes

Xie

Zhao

et al. 2008

Journal of Organometallic Chemistry

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“…[140][141][142] For example, with 2 , 1,1-diphenylacetone was reduced in 2-PrOH under base-free conditions with an ee of 99 % using a S/C ratio as high as 10000. [141] The use of a phase-transfer catalyst, or introduction of sodium sulfonate groups in the ligands, enabled the system to operate in H 2 O/2-PrOH mixtures.…”

Section: Ikariya and Co-workers Prepared The [Ircla C H T U N G T R Ementioning

confidence: 99%

Enantioselective Synthesis of Alcohols and Amines by Iridium‐Catalyzed Hydrogenation, Transfer Hydrogenation, and Related Processes

Bartoszewicz

Ahlsten

Martín‐Matute

2013

Chemistry A European J

162

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The preparation of chiral alcohols and amines by using iridium catalysis is reviewed. The methods presented include the reduction of ketones or imines by using hydrogen (hydrogenations), isopropanol, formic acid, or formate (transfer hydrogenations). Also dynamic and oxidative kinetic resolutions leading to chiral alcohols and amines are included. Selected literature reports from early contributions to December 2012 are discussed.

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Highly Efficient Iridium Catalyst for Asymmetric Transfer Hydrogenation of Aromatic Ketones under Base-Free Conditions

Cited by 126 publications

References 23 publications

Improved nucleotide selectivity and termination of 3′-OH unblocked reversible terminators by molecular tuning of 2-nitrobenzyl alkylated HOMedU triphosphates

Improved nucleotide selectivity and termination of 3′-OH unblocked reversible terminators by molecular tuning of 2-nitrobenzyl alkylated HOMedU triphosphates

Theoretical investigation on the mechanisms of transfer hydrogenation of ketones catalyzed by iridium complexes

Enantioselective Synthesis of Alcohols and Amines by Iridium‐Catalyzed Hydrogenation, Transfer Hydrogenation, and Related Processes

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