10488-03-6

Upstream product

• 186581-53-3 diazomethane 
• 23020-15-7 (1S,2S)-2-phenylcyclopropane-1-carboxylic acid 
• 939-89-9 (1S)-2-phenylcyclopropane-1-carboxylic acid 
• 100-42-5 styrene 
• 6832-16-2 methyl diazoacetate 
• 139156-62-0 (1S,2R,3R)-2-(Methoxycarbonyl)-3-phenylcyclopropane-1-carboxylic acid 
• 5685-38-1 2-phenyl-cyclopropanecarboxylic acid 
• 67-56-1 methanol 
• 103-26-4 Methyl cinnamate 
• 292638-85-8 acrylic acid methyl ester 
• 100-39-0 benzyl bromide 
• 97-71-2 ethyl (S,S)-2-phenylcyclopropane-1-carboxylate 
• 19006-47-4 dimethyl 3-phenylpentanedioate 
• 4165-96-2 3-phenylglutaric acid 

Downstream Products

• 110659-58-0 (1S,2S)-trans-1-(hydroxymethyl)-2-phenylcyclopropane 
• 53403-04-6 (+)-(1S,2S)-1-methyl-2-phenylcyclopropane 
• 110659-49-9 (+)-(1'S,2'S)-2-(2'-methylcyclopropyl)aniline 
• 110659-48-8 (1'S,2'S)-1-(2'-methylcyclopropyl)-2-nitrobenzene 
• 29667-46-7 (1S,2R)-2-phenylcyclopropylmethanol 
• 29667-47-8 (+)-(1S,2R)-1-methyl-2-phenylcyclopropane 
• 110659-53-5 (+)-(1'R,2'S)-2-(2'-methylcyclopropyl)aniline 
• 110659-52-4 (1'R,2'S)-1-(2'-methylcyclopropyl)-2-nitrobenzene 

Relevant academic research and scientific papers

Single-chiral bis(oxazolinyl)pyridine (pybox). Efficiency in asymmetric catalytic cyclopropanation

Single-chiral bis(oxazolinyl)pyridine ligands were examined as ligands for ruthenium-catalyzed asymmetric catalytic cyclopropanation of olefins: enantioselectivities up to 94% for the trans-cyclopropane were observed.

Highly enantioselective cyclopropanation of styrenes and diazoacetates catalyzed by 3-oxobutylideneaminatocobalt(II) complexes, part 1. Designs of cobalt complex catalysts and the effects of donating ligands

Highly enantioselective cyclopropanation of styrene derivatives and diazoacetates was effectively catalyzed by reasonably designed 3-oxobutylideneaminatocobalt(II) complexes, whose ligands were prepared from 1,2-dimesitylethyl-enediamine and alkyl 3-oxobutanoates. The steric demand of the diamine unit of the complexes seriously influenced the enantioselectivity, and the ester groups on their side chains somewhat improved the trans-selectivity. Addition of a catalytic amount of N-methylimidazole significantly accelerated the reaction and enhanced the enantioselectivity due to its coordination to the center cobalt atom of the complex as an axial ligand. Alcoholic or aqueous alcoholic solvents were also effective particularly for the cyclopropanation of 1-substituted 1-phenylethylenes to achieve high enantioselectivity in aqueous methanol.

Bis(oxazoline)·copper(I)-catalyzed enantioselective cyclopropanation of cinnamate esters with diazomethane

Chiral bis(oxazoline)-copper(I) complexes were found to be effective catalysts for the enantioselective cyclopropanation reaction of trans-cinnamate esters exploiting an argon flow mediated diazomethane addition method. After optimization of the catalyst structure, good yields and enantiomeric excesses were obtained with electron-poor methyl cinnamate derivatives. Sterically demanding esters gave lower yields and enantioselectivities. The correlation between the product enantiopurities and the σ+ values of the aromatic para-substituents was shown to be linear in a Hammet-type plot.

Highly enantioselective cyclopropanation of styrenes with diazoacetates catalyzed by optically active β-ketoiminato cobalt(II) complexes

The highly enantioselective cyclopropanation of styrenes with diazoacetates was achieved using reasonably designed β-ketoiminato cobalt(II) complex catalysts. In the presence of optically active cobalt(II) complexes derived from optically active 1,2-(2,4,

Chiral Ruthenium(II)-Bis(2-oxazolin-2-yl)pyridine Complexes. Asymmetric Catalytic Cyclopropanation of Olefins and Diazoacetates

A chiral ruthenium(II)-bis(2-oxazolin-2-yl)pyridine catalyst prepared in situ from optically active bis(2-oxazolin-2-yl)pyridine (Pybox-ip) (2) and 2 (1) exhibited efficient activity for the asymmetric cyclopropanation (ACP) of styrene and several diazoacetates to give the corresponding trans- and cis-2-phenylcyclopropane-1-carboxylates (3 and 4) in good yields (66-87percent).A mixture of 1 and 2 in an atmosphere of ethylene produced the trans-RuCl2 (Pybox-ip)(ethylene) complex (5), which also proved to be a poweful catalyst for ACP.The stereoselectivity of the trans- and cis-cyclopropanes were from 90:10 up to 98:2, and their enantioselectivities reached 97percent.A catalytic system with 5 could be used for several olefins and internal olefins.A concerted mechanism of ACP with the Ru-Pybox catalyst was postulated on the basis of the stereospecificity with deuterated styrene.Other substituents, such as ethyl, s-butyl, benzyl, and phenyl on the oxazoline rings of Pybox in place of the isopropyl group were also examined, and were found to exhibit a similar high trans-stereoselection and a high enantioselectivity of the cyclopropane products; ex . with Ru-Pybox-ethyl 91:9 of 3:4 and 82percent ee for 3.The non-chiral Ru-Pybox-dihydro catalyst exhibited asymmetric induction with 39percent ees of 3 with d- and l-menthyl diazoacetates, and kept a high trans- and cis-stereoselection of 97-3.

A new chiral ruthenium complex for catalytic asymmetric cyclopropanation

A new chiral ruthenium complex 6, featured with an N,O-mixed polydentate ligand, was synthesized and characterized. This ruthenium complex showed high efficiency in catalytic cyclopropanations of alkenes with diazoacetates. High trans/cis selectivity and enantioselectivity (up to 96%) were achieved with the readily accessible ethyl diazoacetate as the reagent.

Electrochemical Ring-Opening Dicarboxylation of Strained Carbon-Carbon Single Bonds with CO2: Facile Synthesis of Diacids and Derivatization into Polyesters

Diacids are important monomers in the polymer industry to construct valuable materials. Dicarboxylation of unsaturated bonds, such as alkenes and alkynes, with CO2 has been demonstrated as a promising synthetic method. However, dicarboxylation of C-C single bonds with CO2 has rarely been investigated. Herein we report a novel electrochemical ring-opening dicarboxylation of C-C single bonds in strained rings with CO2. Structurally diverse glutaric acid and adipic acid derivatives were synthesized from substituted cyclopropanes and cyclobutanes in moderate to high yields. In contrast to oxidative ring openings, this is also the first realization of an electroreductive ring-opening reaction of strained rings, including commercialized ones. Control experiments suggested that radical anions and carbanions might be the key intermediates in this reaction. Moreover, this process features high step and atom economy, mild reaction conditions (1 atm, room temperature), good chemoselectivity and functional group tolerance, low electrolyte concentration, and easy derivatization of the products. Furthermore, we conducted polymerization of the corresponding diesters with diols to obtain a potential UV-shielding material with a self-healing function and a fluorine-containing polyester, whose performance tests showed promising applications.

Boronic Acid-Mediated Photocatalysis Enables the Intramolecular Hydroacylation of Olefins Using Carboxylic Acids

An intramolecular hydroacylation of olefins using carboxylic acids (CAs) has been developed. With the aid of a boronic acid, CAs can be used as acyl-radical precursors in catalytic photoredox reactions driven by visible light. The CAs are easily converted into their corresponding cyclic ketones without the need to use any stoichiometric activating reagents. Mechanistic studies implied that the formation of an “ate” complex from the CA and boronic acid is crucial for the generation of the acyl radical equivalent from the unreactive carboxy group.

Green Esterification of Carboxylic Acids Promoted by tert-Butyl Nitrite

In this work, the green esterification of carboxylic acids promoted by tert-butyl nitrite has been well developed. This transformation is compatible with a broad range of substrates and exhibits excellent functional group tolerance. Various drugs and substituted amino acids are applicable to this reaction under near neutral conditions, with good to excellent yields.

Synthesis of a novel C2-symmetric bis-oxazoline (=bis[4,5-dihydrooxazole]) and its application as chiral ligand in asymmetric transition metal catalysis

The new C2-symmetric bis-oxazoline (=bis[4,5-dihydrooxazole]) 2 with a chiral trans-(2R,3R)-2,3-bis(3,5-diphenylphenyl)cyclopropylidene (=trans-(2R,3R)-2,3-bis([1,1′: 3′,1″-terphenyl]-5′-yl) cyclopropylidene) backbone was efficiently synthesized (Scheme). All synthetic steps were easy to perform and led to the desired product in good overall yields. Compound 2 was tested and compared as ligand in several enantioselective catalytic reactions such as palladium(0)-catalyzed enantioselective allylic alkylations and copper(I)-catalyzed enantioselective cyclopropanations and aziridinations. Copyright