15754-20-8

Upstream product

• 15754-21-9 1-phenylethan-1-one O-methyl oxime 
• 10341-75-0 (E)-1-phenylethanone oxime 
• 2181-42-2 trimethylsulphonium iodide 
• 67-62-9 O-Methylhydroxylamin 
• 98-86-2 acetophenone 
• 593-56-6 N-methoxylamine hydrochloride 
• 128796-39-4 4-trifluoromethylphenylboronic acid 
• 142533-52-6 (Z)-2-bromo-1-phenylethanone O-methyl oxime 
• 77561-95-6 (Z)-2-chloro-1-phenylethanone O-methyl oxime 
• 98-80-6 phenylboronic acid 
• 70-11-1 α-bromoacetophenone 
• 532-27-4 1-chloroacetophenone 
• 14221-01-3 tetrakis(triphenylphosphine) palladium⁽⁰⁾ 
• 201230-82-2 carbon monoxide 

Downstream Products

• 2627-86-3 (S)-1-phenyl-ethylamine 
• 3886-69-9 (R)-1-phenyl-ethyl-amine 
• 135923-85-2 O-Methyl-N-((S)-1-phenyl-ethyl)-hydroxylamine 
• 135879-69-5 (R)-O-methyl-N-(α-methylbenzyl)hydroxylamine 
• 618-36-0 rac-methylbenzylamine 
• 130483-52-2 (E)-3-hydroxy-4,4-dimethyl-1-phenylpentan-1-one O-methyl oxime 
• 1581719-55-2 (E)-1-(2-((tert-butyldiphenylsilyl)ethynyl)phenyl)ethanone O-methyl oxime 

Relevant academic research and scientific papers

Synthesis of 14C-labeled S-(-)-1-phenylethylamine and its application to the synthesis of [14C] CI-1021, a potential antiemetic agent(1)

S-(-)-1-[U-ring- 14C]phenylethylamine 3 was synthesized through the enantioselective borane reduction of E-[U-ring-14C]acetophenone oxime methyl ether derived from [U-ring-14C]acetophenone. The overall radiochemical yield was 66.7%. The enantiomeric excess (ee) was 96.60%. Coupling the labeled amine 3 with (R)-N-[(benzo[b]furan-2-ylmethoxy)-carbonyl-2-methyltryptophan 4 provided [R-(R* , S*)] {1-(1H-indole-3-ylmethyl)-1-methyl-2-oxo-2-[(1-[U-ring-14C]phenylethyl) amino]ethyl} carbamic acid benzo[b]furan-2-ylmethyl ester (CI-1021), a potential antiemetic agent.

Catalytic Asymmetric Carbene Transfer Reactions of Diazo Oxime Ethers with Olefins and Their Synthetic Applications

The first catalytic asymmetric cyclopropanation of diazo oxime ethers with olefins was developed. In the presence of a Ru(II)-Pheox catalyst, various optically active cyclopropyl oxime derivatives were obtained in high yields (up to 99%) with high enantioselectivities (up to 98% ee). Furthermore, optically active cyclopropyl oxime ethers could be successfully converted into the corresponding cyclopropyl methylamine derivatives via metal hydride and Grignard reagent mediated Beckmann rearrangement, which are potential candidates for the assessment of biological and pharmaceutical activities.

Rh-Catalyzed N-O Bond Cleavage of Anthranil: A C-H Amination Reagent for Simultaneous Incorporation of Amine and a Functional Group

A novel Rh(III)-catalyzed C-H bond amination with the simultaneous release of a formyl group at distal positions is realized employing anthranil as a new type of C-H amination reagent. This chemistry provides an efficient protocol for the synthesis of 2-a

A facile and versatile electro-reductive system for hydrodefunctionalization under ambient conditions

A general electrochemical system for reductive hydrodefunctionalization is described, employing the inexpensive and easily available triethylamine (Et3N) as a sacrificial reductant. This protocol is characterized by facile operation, sustainable conditions, and exceptionally wide substrate scope covering the cleavage of C-halogen, N-S, N-C, O-S, O-C, C-C and C-N bonds. Notably, the selectivity and capability of reduction can be conveniently switched by simple incorporation or removal of an alcohol as a co-solvent.

Use of Strain-Release for the Diastereoselective Construction of Quaternary Carbon Centers

Herein, we describe the formation of quaternary carbon centers with excellent diastereoselectivity via a strain-release protocol. An organometallic species is generated by Cp*Rh(III)-catalyzed C-H activation, which is then coupled with strained bicyclobut

Photocatalyzed Triplet Sensitization of Oximes Using Visible Light Provides a Route to Nonclassical Beckmann Rearrangement Products

Oximes are valuable synthetic intermediates for the preparation of a variety of functional groups. To date, the stereoselective synthesis of oximes remains a major challenge, as most current synthetic methods either provide mixtures of E and Z isomers or furnish the thermodynamically preferred E isomer. Herein we report a mild and general method to achieve Z isomers of aryl oximes by photoisomerization of oximes via visible-light-mediated energy transfer (EnT) catalysis. Facile access to (Z)-oximes provides opportunities to achieve regio- and chemoselectivity complementary to those of widely used transformations employing oxime starting materials. We show an enhanced one-pot protocol for photocatalyzed oxime isomerization and subsequent Beckmann rearrangement that enables novel reactivity with alkyl groups migrating preferentially over aryl groups, reversing the regioselectivity of the traditional Beckmann reaction. Chemodivergent N- or O- cyclizations of alkenyl oximes are also demonstrated, leading to nitrones or cyclic oxime ethers, respectively.

Palladium-catalyzed C-H activation/C-C cross-coupling reactions: Via electrochemistry

Palladium-catalyzed C-H activation/C-C cross-coupling reactions typically require stoichiometric chemical oxidants and exogenous ligands. However, there are significant disadvantages associated with the use of traditional stoichiometric oxidants. To overcome these issues, we have developed an electrochemical strategy to achieve methylation and acylation.

The synthesis of pyrroles and oxazoles based on gold α-imino carbene complexes

Cationic gold complexes of α-oximimino carbenes have been identified to react with weak nucleophiles including enol ethers and nitriles. These findings allowed us to develop the highly efficient synthesis of pyrroles and oxazoles.

Palladium-catalyzed enolate arylation as a key C-C bond-forming reaction for the synthesis of isoquinolines

The palladium-catalyzed coupling of an enolate with an ortho-functionalized aryl halide (an α-arylation) furnishes a protected 1,5-dicarbonyl moiety that can be cyclized to an isoquinoline with a source of ammonia. This fully regioselective synthetic route tolerates a wide range of substituents, including those that give rise to the traditionally difficult to access electron-deficient isoquinoline skeletons. These two synthetic operations can be combined to give a three-component, one-pot isoquinoline synthesis. Alternatively, cyclization of the intermediates with hydroxylamine hydrochloride engenders direct access to isoquinoline N-oxides; and cyclization with methylamine, gives isoquinolinium salts. Significant diversity is available in the substituents at the C4 position in four-component, one-pot couplings, by either trapping the in situ intermediate after α-arylation with carbon or heteroatom-based electrophiles, or by performing an α,α-heterodiarylation to install aryl groups at this position. The α-arylation of nitrile and ester enolates gives access to 3-amino and 3-hydroxyisoquinolines and the α-arylation of tert-butyl cyanoacetate followed by electrophile trapping, decarboxylation and cyclization, C4-functionalized 3-aminoisoquinolines. An oxime directing group can be used to direct a C-H functionalization/bromination, which allows monofunctionalized rather than difunctionalized aryl precursors to be brought through this synthetic route.

Rhodium(III)-catalyzed coupling of aromatic ketazines or oximes with 2-vinyloxirane via C-H activation

Described herein is a rhodium(III)-catalyzed coupling of aromatic ketazines or oximes with 2-vinyloxirane via directed C-H activation. This reaction proceeds efficiently under mild conditions with a low catalyst loading, especially in conditions with room temperature in the absence of additives for aromatic ketazines. A wide range of substituted substrates is supported and a possible mechanism is proposed according to the experimental results of kinetic isotopic effect, reversibility studies, and catalysis with rhodacycle intermediate c1.