Biomimetic trifunctional organocatalyst showing a great acceleration for the transesterification between vinyl ester and alcohol

Ema, Tadashi; Tanida, Daisuke; Matsukawa, Tatsuya; Sakai, Takashi

doi:10.1039/b718763g

Cited by 38 publications

(32 citation statements)

References 40 publications

(3 reference statements)

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“…[26] Sakai et al constructed a cooperative trifunctional organocatalyst (10) based upon the active site of serine hydrolase for racemic transesterification of vinyl acetates (14) and 2-propanol (Scheme 2). [27] This trifunctional organocatalysis promotes transesterification at low catalyst loading (1 mol-%) at room temperature. Reactions catalysed by 10 at 1 mol-% catalyst loading between 2-propanol and 14 were monitored by 19 F NMR spectroscopy and proceeded with remarkable rate enhancement compared to the uncatalysed reaction (k cat /k uncat = 3.76 ϫ 10 6 ).…”

Section: Trifunctional Organocatalysts and Catalysismentioning

confidence: 99%

“…Biomimetic trifunctional organocatalysts (10) reported by Sakai. [27] organocatalyst (18), activated by benzoic acid, for an azaMorita-Baylis-Hillman (aza-MBH) reaction between methyl vinyl ketone (20) and aryl N-tosyl imines (21) in DCM to yield the MBH adduct 22 (Scheme 3). [28] The reactions proceed, in the presence of benzoic acid, with high yield (up to Ͼ95 %) and enantioselectivity (up to 92 % ee) at room temperature for a range of electron-rich and -deficient aryl N-tosyl imines.…”

Section: Trifunctional Organocatalysts and Catalysismentioning

confidence: 99%

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Trifunctional Organocatalysts: Catalytic Proficiency by Cooperative Activation

Kenny

Liu

2015

Eur J Org Chem

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In this microreview, trifunctional organocatalysts, defined as catalysts with three distinct mechanistic functionalities, are surveyed in order to understand not just catalytic activation but also catalysis orchestration. Related cases in which the mechanistic trifunctionality in catalysis is conferred by more than one singular catalyst are also evaluated. The potential role of highly functionalised organocatalysts toward organized catalysis with more complexity and proficiency is subsequently discussed to anticipate new challenges in biomimetic catalysis.

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Section: Trifunctional Organocatalysts and Catalysismentioning

confidence: 99%

Section: Trifunctional Organocatalysts and Catalysismentioning

confidence: 99%

Trifunctional Organocatalysts: Catalytic Proficiency by Cooperative Activation

Kenny

Liu

2015

Eur J Org Chem

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“…Ema and Sakai constructed a trifunctional system, TF‐1 , capable of truly remarkable rate enhancement. An elegant biomimetic system based upon the active site of serine hydrolase catalyzed transesterification of vinyl acetates (Scheme ) . The catalyst contained a Brønsted base (pyridine), a Lewis base (alcohol) and a Brønsted acid (thiourea).…”

Section: Asymmetric Trifunctional Organocatalysis Of the Mbh Or Aza‐mmentioning

confidence: 99%

Cooperative Trifunctional Organocatalysts for Proficient Proton Transfer Reactions

Kenny

Liu

2016

Chem. Rec.

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Cooperativity is essential to proficient catalysis, and designing biomimetic, cooperative catalysis is a major avenue to finding new and efficient chemical reactions with practical applications. One challenge in designed cooperative catalysis is to access high catalytic proficiency (large enhancement in both rate and enantioselectivity) as seen in biocatalysis. Here described is an approach of developing and investigating trifunctional organocatalysts with three distinct catalytic functionalities, in order to understand how cooperativity could be organized for enantioselective activation that confers the observed proficiency in a tandem Michael-aldol-proton transfer elimination model reaction. This in future may assist in finding not just cooperative but also regulated catalysis to expand the level of catalytic complexity and efficiency in biomimetic systems.

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“…They clearly resemble the enzymatic pockets found in serine proteases for the activation of the amide carbonyl towards the serine nucleophilic attack. Within what is called the "oxyanion hole", the amide carbonyl is coordinated and activated by two NH groups, hence favouring the serine nucleophilic attack with the formation of a tetrahedral intermediate stabilised by H-bonding ( Figure 11) [45,46]. A variety of electrophiles can be activated towards nucleophilic asymmetric addition with the same action mode and a series of reactions have been investigated so far [47,48].…”

Section: Explicit H-bonding Organocatalysismentioning

confidence: 99%

Organocatalysts for enantioselective synthesis of fine chemicals: definitions, trends and developments

Federsel¹

2014

ScienceOpen Research

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Organocatalysis, that is the use of small organic molecules to catalyse organic transformations, has been included among the most successful concepts in asymmetric catalysis and it has been used for the enantioselective construction of C-C, C-N, C-O, C-S, C-P, and C-halide bonds. Since the seminal works in early 2000, the scientific community has been paying an ever-growing attention to the use of organocatalysts for the synthesis, with high yields and remarkable stereoselectivities, of optically active fine chemicals of interest for the pharmaceutical industry. A brief overview is here presented about the two main classes of substrate activation by the catalyst: covalent organocatalysis and non-covalent organocatalysis, with a more stringent focus on some recent outcomes in the field of the latter and of hydrogen-bond-based catalysis. Finally, some successful examples of heterogenisation of organocatalysts are also discussed, in the view of a potential industrial exploitation.

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Biomimetic trifunctional organocatalyst showing a great acceleration for the transesterification between vinyl ester and alcohol

Abstract: Trifunctional organocatalysts and mimicking the active site of serine hydrolases showed high catalytic activity with up to a 3,700,000-fold acceleration for the acyl-transfer reactions from vinyl trifluoroacetate to alcohol.

Cited by 38 publications

References 40 publications

Trifunctional Organocatalysts: Catalytic Proficiency by Cooperative Activation

Trifunctional Organocatalysts: Catalytic Proficiency by Cooperative Activation

Cooperative Trifunctional Organocatalysts for Proficient Proton Transfer Reactions

Organocatalysts for enantioselective synthesis of fine chemicals: definitions, trends and developments

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