Highly Diastereo- and Enantioselective Aldol Reaction of Methyl α-Isocyanoacetate: A Cooperative Catalysis Approach

Kim, Hun Young; Oh, Kyungsoo

doi:10.1021/ol103104y

Cited by 139 publications

(42 citation statements)

References 59 publications

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“…Similarly, the nonsymmetrical organocatalyst 2 26 was prepared by a mechanochemical LAG coupling of 3,5‐bis(trifluoromethyl)phenyl isothiocyanate with 4‐chloroaniline in >99 % yield (Table 1). Again, the absence of the isothiocyanate reactant was readily verified by the absence of the characteristic isothiocyanate stretching band in the spectrum of the mechanochemical product (Figure 1).…”

Section: Resultsmentioning

confidence: 99%

Click Mechanochemistry: Quantitative Synthesis of “Ready to Use” Chiral Organocatalysts by Efficient Two‐Fold Thiourea Coupling to Vicinal Diamines

Štrukil

Igrc

Eckert‐Maksić

et al. 2012

Chemistry A European J

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Mechanochemical methods of neat grinding and liquid-assisted grinding have been applied to the synthesis of mono- and bis(thiourea)s by using the click coupling of aromatic and aliphatic diamines with aromatic isothiocyanates. The ability to modify the reaction conditions allowed the optimization of each reaction, leading to the quantitative formation of chiral bis(thiourea)s with known uses as organocatalysts or anion sensors. Quantitative reaction yields, combined with the fact that mechanochemical reaction conditions avoid the use of bulk solvents, enabled solution-based purification methods (such as chromatography or recrystallization) to be completely avoided. Importantly, by using selected model reactions, we also show that the described mechanochemical reaction procedures can be readily scaled up to at least the one-gram scale. In that way, mechanochemical synthesis provides a facile method to fully transform valuable enantiomerically pure reagents into useful products that can immediately be applied in their designed purpose. This was demonstrated by using some of the mechanochemically prepared reagents as organocatalysts in a model Morita-Baylis-Hillman reaction and as cyanide ion sensors in organic solvents. The use of electronically and sterically hindered ortho-phenylenediamine revealed that mechanochemical reaction conditions can be readily optimized to form either the 1:1 or the 1:2 click-coupling product, demonstrating that reaction stoichiometry can be more efficiently controlled under these conditions than in solution-based syntheses. In this way, it was shown that excellent stoichiometric control by mechanochemistry, previously established for mechanochemical syntheses of cocrystals and coordination polymers, can also be achieved in the context of covalent-bond formation.

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Section: Resultsmentioning

confidence: 99%

Click Mechanochemistry: Quantitative Synthesis of “Ready to Use” Chiral Organocatalysts by Efficient Two‐Fold Thiourea Coupling to Vicinal Diamines

Štrukil

Igrc

Eckert‐Maksić

et al. 2012

Chemistry A European J

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“…Based on these remarks, two very simple ureas 4k and 4l were prepared and assayed as BACE-1 inhibitors. 1,3-Bis(3,5-Bis(trifluoromethyl)phenyl)urea, 4k is well known in the field of organocatalysis [42][43][44][45][46][47][48][49][50] . The two N-H are highly acidic and equivalent in 4k.…”

Section: Resultsmentioning

confidence: 99%

Novel phenyl(thio)ureas bearing (thio)oxothiazoline group as potential BACE-1 inhibitors: synthesis and biological evaluation

Andreoli¹,

Doukara²,

Mehdid³

et al. 2011

Journal of Enzyme Inhibition and Medicinal Chemistry

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“…(25)]. [50] The condensation employs CoI 2 , chiral ligand 74 , and the thiourea organocatalyst 75 . NMR analysis indicates that 75 binds to the isonitrile.…”

Section: Aldol-type Condensationsmentioning

confidence: 99%

Catalytic Isonitrile Insertions and Condensations Initiated by RNC–X Complexation

et al. 2014

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Isonitriles are delicately poised chemical entities capable of being coaxed to react as nucleophiles or electrophiles. Directing this tunable reactivity with metal and non-metal catalysts provides rapid access to a large array of complex nitrogenous structures ideally functionalized for medicinal applications. Isonitrile insertion into transition metal complexes has featured in numerous synthetic and mechanistic studies, leading to rapid deployment of isonitriles in numerous catalytic processes, including multicomponent reactions (MCR). Covering the literature from 1990–2014, the present review collates reaction types to highlight reactivity trends and allow catalyst comparison.

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Highly Diastereo- and Enantioselective Aldol Reaction of Methyl α-Isocyanoacetate: A Cooperative Catalysis Approach

Abstract: The cooperative catalyst activity between a chiral transition-metal catalyst and an achiral organocatalyst has been identified as one of the critical asymmetric reaction optimization components in the highly diastereo- and enantioselective aldol reaction of methyl α-isocyanoacetate.

Cited by 139 publications

References 59 publications

Click Mechanochemistry: Quantitative Synthesis of “Ready to Use” Chiral Organocatalysts by Efficient Two‐Fold Thiourea Coupling to Vicinal Diamines

Click Mechanochemistry: Quantitative Synthesis of “Ready to Use” Chiral Organocatalysts by Efficient Two‐Fold Thiourea Coupling to Vicinal Diamines

Novel phenyl(thio)ureas bearing (thio)oxothiazoline group as potential BACE-1 inhibitors: synthesis and biological evaluation

Catalytic Isonitrile Insertions and Condensations Initiated by RNC–X Complexation

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