Palladium‐Catalyzed Insertion of α‐Diazoesters into Vinyl Halides To Generate α,β‐Unsaturated γ‐Amino Esters

As easy as 1, 2, 3 : A palladium‐catalyzed three‐component coupling generates α,β‐unsaturated γ‐amino acids in a single step (see scheme). The reaction is believed to involve migration of a vinyl substituent to a highly electrophilic palladium carbene. Unlike previous synthetic approaches, this synthesis provides access to γ‐amino acids with non‐natural side chains.

     

Diphenylprolinol Silyl Ether as a Catalyst in an Enantioselective,Catalytic Michael Reaction for the Formation of α,α‐Disubstituted α‐Amino Acid Derivatives

Direct and enantioselective : Diphenylprolinol silyl ether was found to catalyze the direct, asymmetric Michael reaction of 4‐substituted 2‐aryl‐2‐oxazoline‐5‐one and α,β‐unsaturated aldehydes, affording the chiral α,α‐disubstituted α‐amino acid derivatives with excellent enantioselectivity.

     

A Simple and Versatile Re‐Catalyzed Meyer–Schuster Rearrangement of Propargylic Alcohols to α,β‐Unsaturated Carbonyl Compounds

Rhenium does the job! A readily available rhenium complex efficiently catalyzed the direct Meyer–Schuster‐like rearrangement of different alkyl‐ and aryl‐substituted propargylic secondary and tertiary alcohols to the corresponding α,β‐unsaturated compounds, which were produced with virtually complete E stereoselectivity. The reaction proceeded under neutral conditions and no racemization of potentially enolizable stereocenters was observed.

     

Base‐Catalyzed Highly Stereoselective Conversion of γ‐Hydroxy‐α,β‐acetylenic Esters to γ‐Acetoxy Dienoates

A convenient route with high stereo control to γ‐acetoxy dienoates is provided by the reaction of methyl propiolate with aldehydes in the presence of ZnEt₂ and N‐methylimidazole at room temperature, followed by the catalytic conversion of the resulting γ‐hydroxy‐α,β‐acetylenic esters with p‐N,N‐dimethylaminopyridine (DMAP) in acetic anhydride (see scheme).

     

Chemo,stereo, and regioselective addition of α‐(2‐methoxyaryl)‐N‐aryl nitrones to diarylidineacetone: Synthesis of novel isoxazolidines

A new set of 2,3,4,5‐tetrasubstituted isoxazolidines with an α,β‐unsaturated carbonyl function at position 4 has been synthesized. The multicomponent approach and microwave irradiation protocol have also been investigated for the above synthesis.     

Enhanced Electron‐Transfer Properties of Cofacial Porphyrin Dimers through π–π Interactions

π–π assisted : Photoinduced electron transfer from cofacial porphyrin dimers to electron acceptors is prominently accelerated, whereas the back electron transfer is decelerated, relative to the corresponding porphyrin monomer (see figure).

     

Synthesis of α‐Stereogenic Amides and Ketones by Enantioselective Conjugate Addition of 1,4‐Dicarbonyl But‐2‐enes

Constructing α‐stereogenic amides and ketones : The highly regioselective and enantioselective conjugate addition of 1,3‐dicarbonyl compounds to 1,4‐dicarbonyl but‐2‐enes has been developed with the chiral bicyclic guanidine as catalyst (ee values up to 97 %; see scheme).

     

A Convenient Method for the Synthesis of α‐Ethynylphospholes and Modulation of Their π‐Conjugated Systems

Mind the (narrow) gap : α‐Ethynylphospholes generated in situ from the corresponding silyl‐capped precursors were converted into a series of α‐(arylethynyl) phospholes bearing functional substituents as well as an α,α′‐linked terphosphole (see scheme). The terphosphole has a narrow HOMO–LUMO gap owing to efficient π conjugation over the three phosphole rings.

     

Organocatalytic Domino Michael–Knoevenagel Condensation Reaction for the Synthesis of Optically Active 3‐Diethoxyphosphoryl‐2‐oxocyclohex‐3‐enecarboxylates

Versatile dominoes : A novel, organocatalytic, Michael–Knoevenagel condensation domino reaction of ethyl 4‐diethoxyphosphoryl‐3‐oxobutanoate with various aryl‐ and aliphatic‐substituted α,β‐unsaturated aldehydes catalyzed by a chiral diarylprolinol ether has been successfully performed. The reaction proceeds in a highly enantio‐ and diastereoselective manner giving access to optically active 6‐substituted‐3‐diethoxyphosphoryl‐2‐oxocyclohex‐3‐enecarboxylates (see scheme).

     

Catalytic Asymmetric Intramolecular Hydroarylations of ω‐Aryloxy‐ and Arylamino‐Tethered α,β‐Unsaturated Aldehydes

Economical approach : The first organocatalytic asymmetric intramolecular hydroarylation of phenol‐ and aniline‐derived enals offers one of the most straightforward and atom‐economic approaches to enantioriched chromans and tetrahydroquinolines (up to 96 % ee; see scheme).

     

Direct Alkenylation of Indoles with α‐Oxo Ketene Dithioacetals: Efficient Synthesis of Indole Alkaloids Meridianin Derivatives

Let's make 'meri' : Metal‐free direct alkenylation of indoles was realized by acid‐mediated substitution reactions of α‐oxo ketene dithioacetals with indoles in trifluoroacetic acid/dichloromethane, selectively affording β‐indolyl mono‐ and disubstituted α,β‐unsaturated carbonyl compounds (see scheme). Condensation of the indolyl/ketene monothioacetals and guanidine nitrate efficiently produced meridianin derivatives.

     

Catalytic Asymmetric Cycloaddition of Ketenes and Nitroso Compounds: Enantioselective Synthesis of α‐Hydroxycarboxylic Acid Derivatives

The appropriate choice of chiral catalyst and starting materials leads to the synthesis of 1,2‐oxazetidin‐3‐ones by cycloadditions of ketenes with nitroso compounds with very good regioselectivity and enantioselectivity. In addition to serving as potentially bioactive target molecules, the products can be transformed into other important classes of compounds, such as α‐hydroxycarboxylic acid derivatives.

     

Osmabenzenes from Osmacycles Containing an η2‐Coordinated Olefin

Osmabenzenes can be easily synthesized from two η²‐coordinated olefin osmacycles in the presence of benzonitrile by means of facile hydrogen‐transfer conversions (see graphic). Mechanisms for the formation of osmabenzenes are proposed based on DFT calculations.

     

Stable Aziridinium Salts as Versatile Intermediates: Isolation and Regio‐ and Stereoselective Ring‐Opening and Rearrangement

Rock trapping and exploration : Aziridinium bromide salts were discovered serendipitously during bromination of N,N‐dicarboxymethylated β‐amino alcohols. Regiospecific ring‐opening and rearrangement of the isolated, surprisingly stable aziridinium salts produces useful molecules including C‐functionalized oxomorpholines and α,β‐unsaturated amines.

     

Host‐Assisted Guest Self‐Assembly: Enhancement of the Dimerization of Pyronines Y and B by γ‐Cyclodextrin

Buckle up! The dimerization of small fluorescent guests is strongly enhanced in presence of a cyclodextrin host. The host cavity acts like a belt to assist the self‐assembly of guests (see picture). Small variations in the guest structure have significant influence on the stability and geometry of the aggregates.

     

α‐Chiral Acetylenes Having an All‐Carbon Quaternary Center: Phase Transfer Catalyzed Enantioselective α Alkylation of α‐Alkyl‐α‐alkynyl Esters

Going through the phases : The title reaction was found to proceed by an initial base‐mediated isomerization to allenyl esters and subsequent phase transfer catalyzed alkylation at the α position of the ester (see scheme).

     

Tandem Double‐Michael‐Addition/Cyclization/Acyl Migration of 1,4‐Dien‐3‐ones and Ethyl Isocyanoacetate: Stereoselective Synthesis of Pyrrolizidines

Up to four adjacent stereocenters can be formed stereoselectively in the construction of a pyrrolizidine unit through a novel organocatalytic reaction that involves treatment of various dienones with ethyl isocyanoacetate (see scheme; DBU=1,8‐diazabicyclo[5.4.0]undec‐7‐ene). Mechanisms for this atom‐economic, one‐pot synthesis have been proposed.

     

A Synthetic Lectin for O‐Linked β‐N‐Acetylglucosamine

Changing employment : Receptor 1 binds β‐N‐acetylglucosaminyl (β‐GlcNAc) up to 100 times more strongly than it does glucose. This synthetic lectin shows affinities similar to wheat germ agglutinin (WGA), a natural lectin used to bind GlcNAc. Remarkably, 1 is more selective than WGA. It favors especially the glycoside unit in glycopeptide 2 , a model of the serine‐O‐GlcNAc posttranslational protein modification.

     

Structural Basis and Enzymatic Mechanism of the Biosynthesis of C9‐ from C10‐Monoterpenoid Indole Alkaloids

Cutting carbons : The three‐dimensional structure of polyneuridine aldehyde esterase (PNAE) gives insight into the enzymatic mechanism of the biosynthesis of C₉‐ from C₁₀‐monoterpenoid indole alkaloids (see scheme). PNAE is a very substrate‐specific serine esterase. It harbors the catalytic triad S87‐D216‐H244, and is a new member of the α/β‐fold hydrolase superfamily. Its novel function leads to the diversification of alkaloid structures.