145193-16-4

Upstream product

• 1797-74-6 allyl phenylacetate 
• 103-80-0 phenylacetyl chloride 
• 1334313-57-3 (Z)-allyl 2-phenyl-2-(2-tosylhydrazono)acetate 
• 62936-34-9 allyl 2-oxo-2-phenylacetate 
• 611-73-4 Benzoylformic acid 
• 1422530-02-6 C₁₈H₁₈N₂O₄S 
• 121-44-8 triethylamine 
• 103-82-2 phenylacetic acid 

Downstream Products

• 63106-93-4 (1S,5R)-1-phenyl-3-oxabicyclo[3.1.0]hexan-2-one 
• 96847-52-8 (1R,2S)-2-oxo-1-phenyl-3-oxabicyclo[3.1.0]hexane 
• 63106-93-4 1-phenyl-3-oxa-bicyclo[3.1.0]hexan-2-one 
• 1076239-16-1 (2E,4E)-allyl 2,5-diphenylpenta-2,4-dienoate 
• 120585-91-3 allyl 2-methoxy-2-phenylacetate 
• 1422529-98-3 allyl 2-(dimethoxyphosphoryl)-2-phenylacetate 
• 1584158-28-0 allyl 2-phenyl-2-((trifluoromethyl)thio)acetate 
• 1616346-44-1 allyl 3-oxo-1-phenyl-2,3-dihydro-1H-imidazo[1,5-a]indole-1-carboxylate 

Relevant academic research and scientific papers

Enantioselective iron-catalyzed intramolecular cyclopropanation reactions

An iron-catalyzed asymmetric intramolecular cyclopropanation was realized in high yields and excellent enantioselectivity (up to 97% ee) by using the iron complexes of chiral spiro-bisoxazoline ligands as catalysts. The superiority of iron catalysts exhibited in this reaction demonstrated the potential abilities of this sustainable metal in asymmetric carbenoid transformation reactions.

Synthesis of Functionalized Silsesquioxane Nanomaterials by Rhodium-Catalyzed Carbene Insertion into Si?H Bonds

We report carbene insertion into Si?H bonds of polyhedral oligomeric silsesquioxanes (POSS) for the synthesis of highly functionalized siloxane nanomaterials. Dirhodium(II) carboxylates catalyze insertion of aryl-diazoacetates as carbene precursors to afford POSS structures containing both ester and aryl groups as orthogonal functional handles for further derivatization of POSS materials. Four diverse and structurally varied silsesquioxane core scaffolds with one, three, or eight Si?H bonds were evaluated with diazo reactants to produce a total of 20 new POSS compounds. Novel diazo compounds containing a fluorinated octyl group and boron-dipyrromethene (BODIPY) chromophore demonstrate the use of highly functionalized substrates. Transformations of aryl(ester)-functionalized POSS compounds derived from this method are demonstrated, including ester hydrolysis and Suzuki–Miyaura cross-coupling.

Photoinduced Diverse Reactivity of Diazo Compounds with Nitrosoarenes

A diverse reactivity of diazo compounds with nitrosoarene in an oxygen-transfer process and a formal [2 + 2] cycloaddition is reported. Nitosoarene has been exploited as a mild oxygen source to oxidize an in situ generated carbene intermediate under visible-light irradiation. UV-light-mediated in situ generated ketenes react with nitosoarenes to deliver oxazetidine derivatives. These operationally simple processes exemplify a transition-metal-free and catalyst-free protocol to give structurally diverse α-ketoesters or oxazetidines.

Tandem Insertion/[3,3]-Sigmatropic Rearrangement Involving the Formation of Silyl Ketene Acetals by Insertion of Rhodium Carbenes into S-Si Bonds

Allyl 2-diazo-2-phenylacetates are shown to react with trimethylsilyl thioethers in the presence of rhodium(II) catalysts to generate α-allyl-α-thio silyl esters. The transformation involves a tandem process involving formal rhodium-catalyzed insertion of the carbene group into the S-Si bond to generate a silyl ketene acetal, followed by a spontaneous Ireland-Claisen rearrangement. The silyl ester products were isolated as the corresponding carboxylic acids after aqueous workup. Intramolecular cyclopropanation of the allyl fragment generally competes with addition of the heteroatom to the carbene center. The reaction occurs under mild conditions and in high yield, allowing for rapid entry into rearrangement tetrasubstituted products. Propargyl esters were shown to generate the corresponding α-allenyl products.

Photochemical Doyle-Kirmse Reaction: A Route to Allenes

This Letter describes the metal-free, blue-light-induced [2,3]-sigmatropic rearrangement of sulfonium ylides generated from donor/acceptor diazoalkanes and propargyl sulfides. The reaction furnishes highly functionalized allenes from a broad range of starting materials in decent yield. Mechanistic experiments supported by the literature data suggest singlet carbenes as intermediates in this reaction.

Catalytic O-H bond insertion reactions using surface modified sewage sludge as a catalyst

Developing a greener, sustainable catalyst is a very important but challenging task in organic synthesis. Herein, for the first time, we choose more economical and greener surface modified sewage sludge-derived carbonaceous materials (SW) treated by perch

Catalytic C-C coupling of diazo compounds with arylboronic acids: Using surface modified sewage sludge as catalyst

A green, mild and efficient synthesis of diarylmethines using sewage sludge-derived carbonaceous materials (SW) by perchloric acid catalyzed coupling reactions between diazo compounds and arylboronic acids was developed. The reaction shows a high level of functional tolerance and a broad substrate scope. Furthermore, the highly selective 1,2-alkyl shift products were furnished through the sterically demanding R4, R5 migration of diazo compounds (3-diazochromanone). The structures of 1,2-shift products have been further confirmed by single-crystal X-ray analysis. Significantly, the synthesis of the core structures of darifenacin (a clinical drug for overactive bladder syndrome, OAB) and diclofensine (a stimulant drug showing antidepressant and monoamine reuptake inhibitor activity) further demonstrated the efficacy and synthetic potential of this method. This journal is

Copper-catalyzed carbene insertion and ester migration for the synthesis of polysubstituted pyrroles

Copper-catalyzed carbene insertion/ester migration/cyclization of enaminones and α-diazo compounds occurred efficiently to afford 2-ester polysubstituted pyrroles under mild conditions in moderate-to-good yields. Substituent functionality was well tolerated and13C-labelled experiments demonstrated 1,2-ester migration during the reaction.

Visible-Light-Mediated S?H Bond Insertion Reactions of Diazoalkanes with Cysteine Residues in Batch and Flow

We describe the application of S?H bond insertion reactions of aryl diazoacetates with cysteine residues that enabled metal-free, S?H functionalization under visible-light conditions. Moreover, this process could be intensified by a continuous-flow photomicroreactor on the acceleration of the reaction (6.5 min residence time). The batch and flow protocols described were applied to obtain a wide range of functionalized cysteine derivatives and cysteine-containing dipeptides, thus providing a straightforward and general platform for their functionalizations in mild conditions. (Figure presented.).

Preparation of Organic Nitrates from Aryldiazoacetates and Fe(NO3)3·9H2O

A thermal protocol is reported for the formal insertion of nitric acid into aryldiazoacetates using Fe(NO3)3·9H2O. This strategy is mild and high yielding and allows the preparation of a large variety of members of an unprecedented family of organic nitrates. The nitrate group can be also readily transformed into other functional groups and heterocyclic moieties and can possibly allow new biological explorations of untapped potential associated with their NO-releasing ability.