Catalytic Enantioselective Desymmetrization of 1,3-Diazido-2-propanol via Intramolecular Interception of Alkyl Azides with Diazo(aryl)acetates

The first catalytic enantioselective desymmetrization of 1,3-diazido-2-propanol via an intramolecular interception of alkyl azides by Cu–carbenoids has been realized. A wide range of 1,3-diazidoisopropyl diazo­(aryl)­acetates were converted to cyclic α-imino esters in the presence of bisoxazoline ligand (<i>S,S</i>)-Ph-Box with good to excellent yields, and the enantiomeric excess was up to 97%

Correction to Catalytic Enantioselective Desymmetrization of 1,3-Diazido-2-propanol via Intramolecular Interception of Alkyl Azides with Diazo(aryl)acetates

Correction to Catalytic Enantioselective Desymmetrization of 1,3-Diazido-2-propanol via Intramolecular Interception of Alkyl Azides with Diazo(aryl)acetate

Catalytic Enantioselective Desymmetrization of 1,3-Diazido-2-propanol via Intramolecular Interception of Alkyl Azides with Diazo(aryl)acetates

The first catalytic enantioselective desymmetrization of 1,3-diazido-2-propanol via an intramolecular interception of alkyl azides by Cu–carbenoids has been realized. A wide range of 1,3-diazidoisopropyl diazo­(aryl)­acetates were converted to cyclic α-imino esters in the presence of bisoxazoline ligand (<i>S,S</i>)-Ph-Box with good to excellent yields, and the enantiomeric excess was up to 97%

Catalytic Enantioselective Desymmetrization of 1,3-Diazido-2-propanol via Intramolecular Interception of Alkyl Azides with Diazo(aryl)acetates

The first catalytic enantioselective desymmetrization of 1,3-diazido-2-propanol via an intramolecular interception of alkyl azides by Cu–carbenoids has been realized. A wide range of 1,3-diazidoisopropyl diazo­(aryl)­acetates were converted to cyclic α-imino esters in the presence of bisoxazoline ligand (<i>S,S</i>)-Ph-Box with good to excellent yields, and the enantiomeric excess was up to 97%

Asymmetric Intramolecular Desymmetrization of <i>meso</i>-α,α′-Diazido Alcohols with Aryldiazoacetates: Assembly of Chiral C₃ Fragments with Three Continuous Stereocenters

The chiral Cu-complex-catalyzed intramolecular interception of <i>meso</i>-α,α′-diazido alcohols with aryldiazoacetates is explored. Most of the enantioenriched α-imino esters with three continuous stereocenters are produced with good to excellent yield and enantioselectivity, and a chiral pocket model is proposed for rationalization of the asymmetric desymmetrization

La tierra : bosquejos de la vida rural

A designed Tf₂O-promoted intramolecular Schmidt reaction of 2-substituted ω-azido carboxylic acids was demonstrated. Tf₂O was used as an activation reagent for the carboxylic acid, and ω-azido anhydride was in situ generated, releasing a molecular TfOH, which acted as an acid promoter for the Schmidt process. A series of 2-substituted pyrrolidines was produced and acetylated for better purification. The strategy was also efficient for conversion of a 4-substituted ω-azido carboxylic acid to the tricyclic lactam

Preparation of Optically Active <i>cis</i>-Cyclopropane Carboxylates: Cyclopropanation of α‑Silyl Stryenes with Aryldiazoacetates and Desilylation of the Resulting Silyl Cyclopropanes

Optically active <i>cis</i>-cyclopropane carboxylates are prepared via the Rh₂(<i>S</i>-PTAD)₄-catalyzed cyclopropanation of α-silyl styrenes with aryl diazoacetates followed by desilylation of the resulting silyl cyclopropane carboxylates. The conjugation of the aryl ring with CC bond and π stacking are proposed for the stereoselectivity of cyclopropanation, and configuration inversion is observed with the desilylation process

Cyclohexanones by Rh-Mediated Intramolecular C–H Insertion

Some long chain α-aryl α-diazo ketones under Rh catalysis cyclize efficiently to the corresponding cyclohexanones. This is in marked contrast to the cyclizations of α-diazo β-ketoesters, which consistently deliver cyclopentanone products

Preparation of Optically Active <i>cis</i>-Cyclopropane Carboxylates: Cyclopropanation of α‑Silyl Stryenes with Aryldiazoacetates and Desilylation of the Resulting Silyl Cyclopropanes

Optically active <i>cis</i>-cyclopropane carboxylates are prepared via the Rh₂(<i>S</i>-PTAD)₄-catalyzed cyclopropanation of α-silyl styrenes with aryl diazoacetates followed by desilylation of the resulting silyl cyclopropane carboxylates. The conjugation of the aryl ring with CC bond and π stacking are proposed for the stereoselectivity of cyclopropanation, and configuration inversion is observed with the desilylation process

Intramolecular Schmidt Reaction of Acyl Chlorides with Alkyl Azides: Capture of <i>N</i>‑Acyliminium Ion Intermediates with Aromatic rings

Intramolecular Schmidt reaction of acyl chlorides with alkyl azides through <i>N</i>-acyliminium ion intermediates is designed and realized. The intramolecular capture of the intermediates with aromatic rings affords several nitrogen-containing tricyclic skeletons. The important feature of the domino process is the efficiency in bond reorganization and ring formation