An efficient method has been developed for direct amide bond synthesis between carboxylic acids and amines via (2-(thiophen-2-ylmethyl)phenyl)boronic acid as a highly active bench-stable catalyst. This catalyst was found to be very effective at room temperature large range of substrates with slightly higher temperatures required challenging ones. methodology can applied aliphatic, α-hydroxyl, aromatic, heteroaromatic well primary, secondary, heterocyclic, even functionalized amines. Notably,...

A syn-enantioselective aldol reaction has been developed using Brønsted acid catalysis based on H(8)-BINOL-derived phosphoric acids. This method affords an efficient synthesis of various beta-hydroxy ketones, some which could not be synthesized enamine organocatalysis.

2-Chlorophenylborinic acid is reported to catalyze dipeptide synthesis in the presence of molecular sieves with no racemization.

Abstract A highly efficient and mild transamidation of amides with amines co‐catalysed by borinic acid acetic has been reported. wide range functionalised formamides was synthesized in excellent yields, including important chiral α‐amino derivatives, minor racemisation being observed. Experiments suggested that the reaction rely on a cooperative catalysis involving an enhanced boron‐derived Lewis acidity rather than improved Brønsted acid.

This short review highlights recent advances in amide reductions. The last two years have witnessed important developments with milestones reached catalytic hydrogenations and hydrosilylations. While metal-catalyzed processes still focus tremendous efforts from the scientific community, methodologies based on metal-free hydrosilylation of amides definitively joined competition. 1 Introduction 2 Recent Use Stoichiometric Reducing Reagents 3 Hydrogenations 4 Hydrosilylations 5 Conclusion Outlook

Abstract An unprecedented spontaneous reactivity between diazonium salts and diboronic acid has been unveiled, leading to a versatile arylboronic synthesis directly from (hetero)arylamines. This fast reaction (35 min overall) tolerates wide range of functional groups is carried out under very mild conditions. The radical nature the mechanism investigated.

Abstract The enantioselective decarboxylative protonation (EDP) of malonic or acetoacetic acid derivatives is a synthetic methodology by which the chirality product generated during enol/enolate step. Although EDP century‐old reaction, it has not received much attention until recently. This review focuses on as an alternative to strong‐base‐mediated deprotonation/asymmetric reprotonation for stereocontrol C–H bond formation. diverse approaches are classified according type catalysis used,...

A reduction of various aryl, alkyl, and α,β-unsaturated amides with phenylsilane, catalysed by a borinic acid, is reported. The unprecedented reaction was carried out under very mild conditions led to useful amines. Furthermore, the tolerates variety functional groups. Initial investigations implicated that an intermediate diarylhydroborane involved in mechanism.

Mannich-type reactions of a glyoxylate imine with carbonyl compounds catalyzed by 3-trifluoromethanesulfonamidopyrrolidine proceed high yields and anti-stereoselectivity. The catalyst is easily prepared the transformation appears to be quite general accommodating aldehydes or ketones.

[reaction: see text] Terminal alumination of alkynes by DIBALH or trimethylaluminum can be performed in a simple manner the presence small amount triethylamine. This new Lewis-base-catalyzed process delivers mixed alkynyldialkylalanes great interest, without need an initial deprotonation step with lithium sodium derivatives followed transmetalation.

By using the powerful N-cumylsulfonamide directed metalation group (DMG), a series of 2-substituted derivatives were prepared according to ortho (DoM) tactic (Table 1). Mild conditions for N-decumylation and other simple transformations products have been achieved (Scheme 2). The 3-silyloxy sultam 12 undergoes further DoM give formyl, thiomethyl, iodo, amide 13a−g potential value saccharin synthesis An effective route target 7-aryl saccharins via Suzuki cross coupling 3) followed by...

Abstract A new sequential two‐step multicatalytic strategy is presented consisting in the efficient DBU‐catalysed trichloroacetimidation of an alcohol followed by a ditriflylamine (Tf 2 NH)‐catalysed intermolecular alkylation silicon‐based nucleophiles and CH nucleophiles. The distinct feature trichloroacetimidate group allows use weaker acid catalysts such as 1,1′‐bi‐2‐naphthol (BINOL)‐derived phosphoric acid, pointing out possible development enantioselective variant. This unprecedented...

On the basis of our recently reported aniline aqueous borylation, molecular diversity was achieved in a one-pot process by combining other reactions such as esterification, Suzuki–Miyaura coupling, hydrogenolysis, or Petasis borono-Mannich.

The domino anionic fragmentation of 2-nitrophenyl-1,3-cyclohexanediones containing an electrophilic appendage such as aldehyde and epoxide is disclosed. This reaction, initiated by a series nucleophiles, involves the generation intermediate hydroxylate followed regioselective formation lactolate into enolate. strategy, devoid any protecting group, enlarges initial ring provides original access to decorated 9-membered lactones with fused indole unit.

Phenylsilane was reevaluated as a useful coupling reagent for amide synthesis. At room temperature, wide range of amides and peptides were obtained in good to excellent yields (up 99 %). For the first time, Weinreb synthesis mediated by hydrosilane also documented. Comparative experiments with various acetoxysilanes suggested involvement phenyl‐triacyloxysilane. From this mechanistic study, silicon tetraacetate shown an efficient amine acylating agent.

Abstract This study outlines the development of novel boronic acids as catalysts for direct synthesis amides from carboxylic and amines. The Lewis acidity was estimated by means computational techniques, observed increase in catalytic activity corroborated kinetic data derived a model reaction. Our investigations led to discovery set ortho‐(sulfonyloxy)benzeneboronic that compared favorably with established state‐of‐the‐art. These newly developed demonstrated efficacy coupling aliphatic,...

Various oxazolidines prepared in two steps from (R)-phenylglycinol react at 0 °C with dialkylalkynylalane−triethylamine complexes the presence of trimethylaluminum high yield and diastereoselectivity. Enantiomerically pure primary α-substituted propargylamines can be easily obtained after removal ferrocenylmethyl protective group under smooth acidic conditions oxidative cleavage chiral appendage.

Reaction of N,N-dibenzyl-O-methylsulfonyl serine methyl ester with a variety heteronucleophiles (sodium azide, sodium phthalimide, amines, thiols) and carbanions malonate) gave, via an aziridinium intermediate, the corresponding β-amino or α,β-diamino in good to excellent yield. A short synthesis orthogonally protected enantiomerically pure 2,3-diamino propionate (Dap) is described.

Abstract The general reduction of phosphine oxides, sulfoxides, and amine N ‐oxides was achieved by combining bis(2‐chlorophenyl)borinic acid with phenylsilane. reaction shown to tolerate a wide range substrates could be performed under mild conditions, only 2.5 mol % the easily synthesized catalyst. Mechanistic investigations pointed key borohydride as real catalyst at precatalyst.