32346-06-8

Upstream product

• 40195-27-5 (1-methoxy-2-phenylvinyloxy)trimethylsilane 
• 27607-77-8 trimethylsilyl trifluoromethanesulfonate 
• 101-41-7 benzeneacetic acid methyl ester 
• 75-77-4 chloro-trimethyl-silane 

Downstream Products

• 96745-91-4 2-(methoxycarbonyl)-2-phenyl-3,6-dihydro-4,5-dimethyl-2H-thiapyran 1-oxide 
• 2904-95-2 methyl threo-2,3-diphenyl-3-(N-phenylamino)propionate 
• 2904-95-2 methyl erythro-2,3-diphenyl-3-(N-phenylamino)propionate 
• 1025761-86-7 methyl 3-(1H-indazol-5-yl)-2,3-diphenylpropanoate 
• 75413-38-6 methyl phenyl<6-(1,2,3,4-tetrahydronaphthalene)>acetate 
• 4358-87-6 (RS)-methyl mandelate 
• 68521-59-5 methyl 2-phenyl-2-thiocyanatoethanoate 
• 3558-61-0 methyl 2-methoxy-2-phenylacetate 
• 120017-07-4 2,3-Diphenyl-3-trimethylsilanyloxy-propionic acid methyl ester 
• 98810-54-9 3-phenyl-4-(trimethylsilylethynyl)azetidin-2-one 
• 98810-54-9 3-phenyl-4-(trimethylsilylethynyl)azetidin-2-one 
• 344864-87-5 3-Methoxycarbonylamino-4-methyl-2-phenyl-pentanoic acid methyl ester 
• 93472-21-0 2-(Methoxycarbonyl-phenyl-methyl)-thiazole-3-carboxylic acid ethyl ester 
• 79380-11-3 3-(Benzyloxycarbonyl-methyl-amino)-2,2-dimethyl-propionic acid methyl ester 

Relevant academic research and scientific papers

Structural Study of Methyl and tert-Butyl Phenylacetate Enolates in Solution: Spectroscopic Determination of Their E or Z Configuration

The structures of Li and K methyl and tert-butyl phenylacetate enolates A,M and B,M have been examined by IR and 13C NMR spectroscopy in different solvents and solvent mixtures.In the IR, coupling of the 8a (or 8b) aromatic ring mode with the ν(C radical

Stereochemistry of the enolate from methyl phenylacetate

Deprotonation of methyl phenylacetate with lithium diisopropylamide in tetrahydrofuran followed by trapping with trimethylsilyl chloride afforded an 81:19 mixture of E- and Z-silyl ketene acetals in agreement with a prediction by the calculation by Dauben

Asymmetric syntheses of nakinadine D, nakinadine E, and nakinadine F: Confirmation of their relative (RS, SR)-configurations and proposal of their absolute (2 S,3 R)-configurations

The syn- and anti-diastereoisomeric forms of the reported structures of the marine alkaloids nakinadines D-F have been synthesized, for the first time in all cases, via an approach involving asymmetric Mannich-type (imino-aldol) reactions of methyl phenylacetate with N-tert-butylsulfinyl imines as the key steps to control the stereochemistry. Comparison of the 1H and 13C NMR spectroscopic data reported for the natural materials with those acquired for these synthetic samples confirms the initially assigned relative (RS,SR)-configurations of these three alkaloids. In the absence of specific rotation (or other diagnostic) data for the natural materials, it is not possible to unambiguously assign their absolute configurations, although given the absolute (2S)-configurations assigned to nakinadines B and C, and the absolute (2S,3R)-configuration previously established for nakinadine A, the data herein uphold our proposal that nakinadines D-F share the absolute (2S,3R)-configuration.

Synthetic strategies for the synthesis and transformation of substituted pyrrolinones as advanced intermediates for rhazinilam analogues

The biaryl core structure of rhazinilam with its fixed dihedral angle is a pivotal element for its unique in vitro cytotoxic activity. Most of the related natural products are oxidized versions of rhazinilam. Replacing the sensitive pyrrole ring by a pyrrolinone ring is the basis of our initial strategy towards rhazinilam analogues. With this goal, variants of the sequence crossed Mukaiyama aldol reaction followed by the Staudinger reaction were studied. Reacting a suitably substituted acetophenone with O-methyl O-trimethylsilyl ketene acetal gave pyrrolinones 8a and 8b in good to excellent yields. These intermediates could be transformed in four high-yielding steps into the pyrrolic precursors 7a-c containing all the atoms necessary for the construction of rings A, B, and C of rhazinilam. Our studies illustrate a lack of stability of these intermediates. Alternative synthetic approaches towards this central biaryl core structure are described.

Copper-catalyzed amination of silyl ketene acetals with N-chloroamines

A copper(I)/2,2′-bipyridyl complex catalyzes an amination reaction of silyl ketene acetals with N-chloroamines, presenting a new preparative method of α-amino esters.

Highly enantioselective mannich reactions with α-aryl silyl ketene acetals and imines

Mannich reactions with chiral silicon Lewis acid activated acylhydrazones and α-aryl silyl ketene acetals and α-aryl,α-alkyl silyl ketene imines proceed efficiently and with good to excellent levels of both diastereoselectivity and enantioselectivity. The reactions provide access to α-aryl,β-hydrazido esters and α-aryl,α-alkyl,β- hydrazido nitriles, which are valuable analogs of β-amino acids.

A practical protocol for the highly E-selective formation of aryl-substituted silylketene acetals

The E/Z-selectivity in the formation of silylketene acetals derived from phenylacetate esters, mediated by LiHMDS, has been studied by in situ NMR techniques. The formation is seen to be highly E-selective with use of the newly developed protocol. Isolated aryl-substituted silylketene acetals are now attainable with high levels of E-geometrical purity in excellent yield.

MODULATORS OF GLUCOCORTICOID RECEPTOR, AP-1, AND/OR NF-κB ACTIVITY AND USE THEREOF

Novel non-steroidal compounds are provided which are useful in treating diseases associated with modulation of the glucocorticoid receptor, and/or AP-1, and/or NF-κB activity including inflammatory and immune diseases, obesity and diabetes having the structure of formula (I), its enantiomers, diastereomers, or a pharmaceutically-acceptable salt, or hydrate, thereof, wherein (Ia) is heterocycle or heteroaryl; J, Ja, E, F, G, Ma, M, Q, Za and Z are as defined herein. Also provided are pharmaceutical compositions and methods of treating inflammatory- or immune-associated diseases and obesity and diabetes employing said compounds.

Uncatalyzed reaction of silyl ketene acetals with oxalyl chloride: A straightforward preparation of symmetrical pulvinic acids

(Chemical Equation Presented) Several natural pulvinic acids were synthesized. Silyl ketene acetals derived from methyl arylacetates (4 equiv) reacted with oxalyl chloride at -78°C, without the need of adding a catalyst. After treatment of the crude diketones with DBU and acidification with hydrochloric acid, symmetrical pulvinic acids methyl esters were obtained. Saponification of the methyl esters afforded the corresponding pulvinic acids in 60-70% overall yields from oxalyl chloride.

Tandem 1,4-addition reactions with benzene and alkylated benzenes promoted by pentaammineosmium(II)

Electrophiles such as dimethoxymethane and 3-penten-2-one react with the complex [Os(NH3)5-(η2-benzene)]2+ in the presence of triflic acid to form metastable benzenium intermediates. These benzenium intermediates further react with carbon nucleophiles including silyl ketene acetals, (silyloxy)alkenes, and phenyllithium in an overall tandem 1,4-addition sequence. The metal fragment controls the relative stereo- and regiochemistry for both electrophilic and nucleophilic addition steps. Upon oxidative demetalation with silver triflate, cis-1,4 cyclohexadienes are formed in yields ranging from 16 to 82%. This methodology can also be used to dearomatize toluene and ortho- and meta-xylene with unexpectedly high regio- and stereocontrol.