Enantioselective Mukaiyama Aldol Reaction Research Articles

A Cu-BOX catalysed enantioselective Mukaiyama-aldol reaction with difluorinated silyl enol ethers and acylpyridine N-oxides.

A Cu(II)/BOX complex catalyses the enantioselective addition of difluorinated silyl enol ethers to acylpyridine N-oxides. The reaction provides difluorinated chiral tertiary alcohols of great interest in medicinal chemistry. These compounds are obtained in moderate to excellent yields and with high enantioselectivities. The stereochemical outcome of the reaction has been explained by DFT calculations.

Copper‐Catalyzed Enantioselective Mukaiyama Aldol Reaction of Silyl Enol Ethers with Isatin‐Derived Oxindolyl β,γ‐Unsaturated α‐Keto Esters

AbstractEnantioselective Mukaiyama 1,2 addition of silyl enol ethers with oxindolyl β,γ‐unsaturated α‐keto esters was developed under catalysis of a chiral L−Cu complex. The reaction was carried out rapidly under mild conditions, to give rise to a series of chiral β‐hydroxyl carbonyl compounds bearing oxindolyl backbone skeleton with high yields and excellent enantioselectivities, up to 99 %, as well as moderate to great diastereoselectivities, up to >20 : 1. This method provided an elegant synthesis route for the synthesis of such compounds.

Acetaldehyde Silyl Enol Ethers in Enantioselective Mukaiyama Aldol Reactions: Enzyme-Like Organocatalysis in Action.

Touched for the very first time! It is herein highlighted how acetaldehyde silyl enol ethers undergo enantioselective Mukaiyama aldol reaction with aliphatic and aromatic aldehydes. The chemistry relies on the use of the highly efficient and substrate-selective imidodiphosphorimidate catalyst, which displays some of the features of enzymatic catalysis.

Copper-catalyzed enantioselective Mukaiyama aldol reaction of silyl enol ethers with isatins.

A highly enantioselective Mukaiyama aldol reaction of silyl enol ethers with isatins catalyzed by chiral copper complexes was developed. A series of chiral 3-substituted 3-hydroxy-2-oxindoles bearing a tetra-substituted center could be obtained exclusively with high yields (up to 95%) and excellent enantioselectivities (up to 99%). In particular, water was essential to improve the diastereoselectivity.

ChemInform Abstract: Chiral Broensted Acid as a True Catalyst: Asymmetric Mukaiyama Aldol and Hosomi—Sakurai Allylation Reactions.

AbstractA new chiral BINOL‐derived thiophosphoramide catalyst is prepared and applied for highly diastereo‐ and enantioselective Mukaiyama aldol reactions of various silyl enol ethers with aryl aldehydes.

Chiral Brønsted Acid as a True Catalyst: Asymmetric Mukaiyama Aldol and Hosomi-Sakurai Allylation Reactions.

Highly diastereo- and enantioselective Mukaiyama aldol reaction catalyzed by a new chiral Brønsted acid, N-(perfluorooctanesulfonyl)thiophosphoramide, is described. The perfluorooctyl substituent on the sulfonyl group of the catalyst plays an essential role in the stereoselection. The catalyst also allows the asymmetric Hosomi-Sakurai allylation, which has been considerably challenging due to the low reactivity of allylsilanes. (29)Si and (31)P NMR monitoring reveals the characteristic feature of the thiophosphoramide catalyst, acting as a strong Brønsted acid even in the presence of excess silyl nucleophiles, which cannot be found in other related phosphoric acid analogues.

Back Cover: Pushing the Boundaries of Vinylogous Reactivity: Catalytic Enantioselective Mukaiyama Aldol Reactions of Highly Unsaturated 2-Silyloxyindoles (Chem. Eur. J. 17/2015)

Back Cover: Pushing the Boundaries of Vinylogous Reactivity: Catalytic Enantioselective Mukaiyama Aldol Reactions of Highly Unsaturated 2-Silyloxyindoles (Chem. Eur. J. 17/2015)

Pushing the boundaries of vinylogous reactivity: catalytic enantioselective mukaiyama aldol reactions of highly unsaturated 2-silyloxyindoles.

The first example of catalytic, enantioselective hypervinylogous Mukaiyama aldol reaction (HVMAR) involving multiply unsaturated 2-silyloxyindoles is reported. The reaction utilizes a chiral Lewis base-catalyzed Lewis acid-mediated technology to deliver homoallylic 3-polyenylidene 2-oxindoles with extraordinary levels of regio-, enantio-, and geometrical selectivity. This work highlights a subtle yet decisive influence of the indole N-substituents on the propagation of the vinylogous reactivity space of the donor substrates up to ten bonds away from the origin of the vinylogy effect. Analysis of the (13) C NMR chemical shifts of the C-ω remote site within homologous silyloxyindole donors enabled rationalization of the results and easy qualitative prediction of the HVMAR reactivity/inertia toward a given aldehyde acceptor.

ChemInform Abstract: Iron(II)‐Derived Lewis Acid/Surfactant Combined Catalysis for the Enantioselective Mukaiyama Aldol Reaction in Pure Water.

ChemInformVolume 46, Issue 4 Preparative Organic Chemistry ChemInform Abstract: Iron(II)-Derived Lewis Acid/Surfactant Combined Catalysis for the Enantioselective Mukaiyama Aldol Reaction in Pure Water. Mathieu Lafantaisie, Mathieu Lafantaisie Dep. Chim., Univ. Laval, Quebec City, Que. G1V 0A6, Can.Search for more papers by this authorAnais Mirabaud, Anais Mirabaud Dep. Chim., Univ. Laval, Quebec City, Que. G1V 0A6, Can.Search for more papers by this authorBaptiste Plancq, Baptiste Plancq Dep. Chim., Univ. Laval, Quebec City, Que. G1V 0A6, Can.Search for more papers by this authorThierry Ollevier, Thierry Ollevier Dep. Chim., Univ. Laval, Quebec City, Que. G1V 0A6, Can.Search for more papers by this author Mathieu Lafantaisie, Mathieu Lafantaisie Dep. Chim., Univ. Laval, Quebec City, Que. G1V 0A6, Can.Search for more papers by this authorAnais Mirabaud, Anais Mirabaud Dep. Chim., Univ. Laval, Quebec City, Que. G1V 0A6, Can.Search for more papers by this authorBaptiste Plancq, Baptiste Plancq Dep. Chim., Univ. Laval, Quebec City, Que. G1V 0A6, Can.Search for more papers by this authorThierry Ollevier, Thierry Ollevier Dep. Chim., Univ. Laval, Quebec City, Que. G1V 0A6, Can.Search for more papers by this author First published: 08 January 2015 https://doi.org/10.1002/chin.201504029Citations: 1Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article.Citing Literature Volume46, Issue4January, 2015 RelatedInformation

Iron(II)‐Derived Lewis Acid/Surfactant Combined Catalysis for the Enantioselective Mukaiyama Aldol Reaction in Pure Water

AbstractThe catalytic asymmetric Mukaiyama aldol reaction in pure water was performed by using a combination of iron(II) dodecyl sulfate, a chiral bipyridine ligand, and benzoic acid. By using the obtained iron(II)‐derived Lewis acid/surfactant combined catalyst, the desired products were afforded in good yields with high diastereo‐ and enantioselectivities.

Synthesis, spectroscopic characterization, and reactivity of water-tolerant Eu3+-based precatalysts.

We report the synthesis, spectroscopic characterization, and reactivity of Eu(3+) in the presence of a new set of chiral ligands designed for the aqueous, enantioselective Mukaiyama aldol reaction. Luminescence and NMR measurements were used to characterize the coordination environments of the Eu(3+)-based precatalysts, and this data is compared with yields and stereoselectivities. In addition to structure-function relationships, we found that, in the presence of excess hexadentate ligands, Eu(3+) is coordinatively saturated, and subsequently, the reactivity of the precatalysts is reduced. These findings are helpful for the design of new ligands that bind Eu(3+) without saturating the Eu(3+) coordination sphere.

An Enantioselective Mukaiyama Aldol Reaction as the Key Step towards the Tetrahydropyran Core of Psymberin via a γ-Butyrolactone Intermediate

We report an alternative synthetic route towards the tetrahydropyran core of psymberin. The key steps are a catalytic enantioselective Mukaiyama aldol reaction and a syn reduction, which allowed for the rapid assembly of a γ-lactone as a precursor for the central fragment of the natural product.

ChemInform Abstract: Highly Enantioselective Mukaiyama Aldol Reaction in Aqueous Conditions Using a Chiral Iron(II) Bipyridine Catalyst.

AbstractThe Fe‐catalyzed Mukaiyama aldol reaction of aromatic silyl enol ethers with aldehydes proceeds in aqueous solvent to give the product β‐hydroxy ketones (III) and (V) with moderate to high diastereo‐ and enantioselectivities (up to 98% e.e.

Iron-Catalyzed Enantioselective Mukaiyama Aldol Reaction

Iron-Catalyzed Enantioselective Mukaiyama Aldol Reaction

Enantioselective Mukaiyama-Aldol Reaction between Enol Silanes and Ketomalonate Catalyzed by the Copper(II) Complex of TIPS-Substituted Bis-oxazoline

Enantioselective Mukaiyama-Aldol Reaction between Enol Silanes and Ketomalonate Catalyzed by the Copper(II) Complex of TIPS-Substituted Bis-oxazoline

Asymmetric Vinylogous Mukaiyama Aldol Reaction of Aldehyde-Derived Dienolates

Unsaturated aldehydes are exquisite building blocks for further transformations in polyketide synthesis. Besides standard transformations that take advantage of the aldehyde functionality, the conjugate addition of hydrides followed by internal protonation allows access to alpha chiral aldehydes. Even though vinylogous Mukaiyama aldol reactions have been used in natural product syntheses before, the first enantioselective Mukaiyama aldol reaction of aldehyde-derived dienolates is described.

Enantioselective Mukaiyama Aldol Reactions with Glyoxylates

The enantioselective aldol reaction is among the most useful and well-developed transformations for the synthesis of chiral materials. Despite this, gaps in asymmetric aldol methodology still exist. The authors present the first ­example of a general, highly enantioselective ­Mukaiyama aldol reaction between aryl ketones and glyoxylates. An indium-PyBox complex is used as a chiral Lewis acid to induce asymmetry.

ChemInform Abstract: Highly Enantioselective Mukaiyama Aldol Reactions Catalyzed by a Chiral Oxazaborolidinium Ion: Total Synthesis of (‐)‐Inthomycin C.

AbstractAn efficient and enantioselective Mukaiyama aldol reaction between ketene silyl acetals and a variety of aldehydes is developed using OAB as catalyst.

In(iii)-pybox complex catalyzed enantioselective Mukaiyama aldol reactions between polymeric or hydrated glyoxylates and enolsilanes derived from aryl ketones

A highly efficient In(III)-pybox complex catalyzed enantio-selective Mukaiyama aldol reaction between polymeric or hydrated glyoxylates and enolsilanes derived from aryl ketones is described. Excellent enantioselectivities, diastereoselectivities and yields were obtained with a broad substrate scope. The mild reaction conditions and simple operation make this methodology very practical.

Highly Enantioselective Mukaiyama Aldol Reactions Catalyzed by a Chiral Oxazaborolidinium Ion: Total Synthesis of (−)-Inthomycin C

A cationic oxazaborolidinium-catalyzed asymmetric Mukaiyama aldol reaction of (1-methoxy-2-methyl-propenyloxy)-trimethylsilane with various aldehydes including α,β-disubstituted acroleins has been developed in high yields and enantioselectivities. The synthetic utility of this methodology was demonstrated in the first short synthesis of naturally occurring inthomycin C in high enantiopurity.