Methyl benzoyl formate

Table 42.3 Enantioselective hydrogenation of methyl benzoyl formate using [Rh(COD) (L-L)][OTf] SHB catalysts supported on Davison silicas of different pore sizes [28]. 

The sulfinyl chirality has shown [86] considerable utility in asymmetric synthesis, particularly for carbon-carbon bond formation (see Sections 2.6.2 and 4.2.8). Its use as the chiral source in a NADH mimic has been reported [240]. Reduction of methyl benzoyl formate by enantiopure l-propyl-(S)-3-(p)-tolyl)sulfinyl-l,4-dihydropyridine yielded the (/ )-mandelate with 96% e.e. 

Asymmetric reduction of carbonyls has also been achieved by Dupas and coworkers by reaction of achiral NADH equivalents mediated by chiral aluminum Lewis acids [23]. They reduced methyl benzoyl formate with the dihydropyrido[2,3-h]indole 86 and chiral aluminum Lewis acids whose structures are drawn and 89 and 90 (Sch. 12). Asymmetric induction was quite low. Details of the reaction, including the conditions used, were not provided nor were the procedures used for the preparation of the chiral Lewis acids 89 and 90. 

Liquid-phase enantioselective hydrogenations of a-ketoesters by alkaloid-modified Pt has been investigated intensively and reviewed. " The first reported reactions of this type were the hydrogenations of methyl pyruvate, MeCOCOOMe, and of methyl benzoyl formate, PhCOCOOMe, over Pt modified by the cinchona alkaloids." ... 

Romanian scientists compared one-electron transfer reactions from triphenylmethyl or 2-methyl benzoyl chloride to nitrobenzene in thermal (210°C) conditions and on ultrasonic stimulation at 50°C (lancu et al. 1992, Vinatoru et al. 1994, Chivu et al. 2006). In the first step, the chloride cation-radical and the nitrobenzene anion-radicals are formed. In the thermal and acoustic variants, the reactions lead to the same set of products with one important exception The thermal reaction results in the formation of HCl, whereas ultrasonic stimulation results in CI2 evolution. At present, it is difficult to elucidate the mechanisms behind these two reactions. As an important conclusion, the sonochemical process goes through the inner-sphere electron transfer. The outer-sphere electron transfer mechanism is operative in the thermally induced process. 

Breuer s group also observed the participation of the Beckmann rearrangement in the decomposition of the (E)-oxime of methyl (benzoyl)phenylphosphinate with the formation of the methyl A-benzoyl-P-phenylphosphonic amide 128 as the sole product the (Z)-oxime 129 decomposed to benzonitrile, methyl hydrogen phenylphosphonate and the carbamylphosphinate 130. 

As has been revealed in the reduction of methyl or ethyl benzoyl-formate with Me PNPH, where the reduction takes place in only one... 

Derivative Formation. Hydrogen peroxide is an important reagent in the manufacture of organic peroxides, including tert-huty hydroperoxide, benzoyl peroxide, peroxyacetic acid, esters such as tert-huty peroxyacetate, and ketone derivatives such as methyl ethyl ketone peroxide. These are used as polymerization catalysts, cross-linking agents, and oxidants (see Peroxides and peroxide compounds). 

If, however, the /7-nitrophenyl ester of iV-henzoyl-L-leucine is treated with 1-methyl-piperidine in chloroform for 30 min and then coupled with glycine ethyl ester, the dipeptide isolated is almost completely racemic. Furthermore, treatment of the p-nitrophenyl ester of iV-benzoyl-L-leucine with 1-methylpiperidine alone leads to the formation of a crystalline material, C13H15NO2, having strong IR bands at 1832 and 1664 cm . Explain these observations, and suggest a reasonable stmcture for the crystalline product. 

Auwers and others soon discovered that the transformation 3 —> 6 did not consistently give flavonols such as 2. For example, alcoholic alkali treatment of dibromide 11 produced 2-benzoyl-benzofuran-3-one 12 instead of the corresponding flavonol. The same observation was made by Robert Robinson in a failed attempt to make datiscetin in 19257 It has reported that when there is a meta (to the coumarone ring oxygen) substituent such as methyl or methoxy, flavonol formation is hindered, whereas methyl, methoxy, and chlorine substituents at the ortho and para positions are conducive to flavonol formation. ... 

Methyl propiolate and pyridine give a rather unstable 2 1 molar adduct which is the 1,2-dihydropyridine (112). The reaction sequence proposed to account for its formation is identical in principle to a similar scheme proposed earlier in the acridine series (Section II,A,2) and is also supported by the observation that the 1-benzoyl-pyridinium cation with the phenylacetylide anion yields (113). ... 

The nitration of l,2,5-selenadiazolo[3,4-/] quinoline 77 with benzoyl nitrate affords the 8-nitro derivative 78, whereas methylation with methyl iodide or methyl sulfate afforded the corresponding 6-pyridinium methiodide 79 or methosulfate 80, respectively (Scheme 29). The pyridinium salt 80 was submitted to oxidation with potassium hexacyanoferrate and provided 7-oxo-6,7-dihydro derivative 81 or, by reaction of pyridinium salt 79 with phenylmagnesium bromide, the 7-phenyl-6,7-dihydro derivative 82. Nucleophilic substitution of the methiodide 79 with potassium cyanide resulted in the formation of 9-cyano-6,9-dihydroderivative 83, which can be oxidized by iodine to 9-cyano-l,2,5-selenadiazolo [3,4-/]quinoline methiodide 84. All the reactions proceeded in moderate yields (81IJC648). 

Another internal acetal, methyl 2-0-benzoyl-3,4-0-benzylidene-/ -D-arabinopyranoside 103 (84), behaves in an analogous manner, except that the isomeric 4-bromo (104) and 3-bromo (105) benzoate derivatives are formed in a ratio of 1 1. The identity of 104 (l-xylo) can be deduced from its mode of formation from a presumed benzoxonium ion (106)... 

Dichloromethyl methyl ether has been prepared by the chlorination of chlorodimethyl ether in the liquid5-4 or gas phase,5 by the reaction of chlorodimethyl ether with sulfuryl chloride and benzoyl peroxide,6 7 and by the treatment of methyl formate with phosphorus pentachloride.8-10... 

The catechol-type ligand appears to be restricted to siderochromes derived from prokaryotic microorganisms. Klebsiella oxytoca, an organism closely related to members of the genus Aerobacter, forms the 2,3-dihy-droxy-N-benzoyl derivates of serine and threonine in three day cultures (72). It is not known if the latter amino acid occurs in trimers but examination of space-filling CPK models does indicate that enterobactin could accomodate a methyl substituent on the carbon of the serine residue. Catechols occur in higher protist organisms but their formation... 

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