S-Formylation

Ci,H 7N04S2 138890-87-6) see Brinzolamide 3,7,ll-trimethyl-2,6,10-dodecatrienol (C]5H260 4602-84-0) see Indometacin farnesil 2,2,8-trimethyl-S-formyl-4H-pyrido[3,4-d]-l,3-dioxane (C, H 3N03 6560-65-2) see Cicletanine... 

Enantiopure a-amino aldehydes are valuable synthons in natural product synthesis [57]. However, problems are often encountered with their configurational instability [58]. Aziridine-2-carboxaldehydes are also a-amino aldehydes and accordingly have a potential synthetic value. We found that M-tritylaziridine-2-carboxaldehyde 56 is a perfectly stable compound and therefore comparable to Garner s aldehyde (ferf-butyl 2,2-dimethyl-4-(S)-formyl-oxazolidine-3-car-boxylate). Aldehyde 56 can readily be prepared from aziridine-2-carboxylic ester 12 by the sequence shown in Scheme 42 [59]. 

A novel masked S-formylation of electron-deficient olefins with 1,3-dioxolane in the presence of (n-Bu4N)2S20g has been observed. Thus when cyclic a,-unsaturated ketones, esters and sulfonyl alkenes react with (n-Bu4N)2S20g in 1,3-dioxolane, the corresponding 1,3-dioxolanyl adducts are obtained in excellent yields (equation 28). 

All three solutions showed the presence (NMR) of the same boron intermediates. In light of this evidence, it was clear that Johnson et al. could not obtain a grant in Europe of valid patent claims to boron intermediates that would be an impediment to us. (Incidentally, for the same reason, Schering could not obtain such intermediate claims.) On the other hand, the Johnson et al. methyl tropate reduction process was patentable over the disclosed Choi diethyl phenylmalonate reduction process and Schering s formyl phenylacetate process was patentable over both the disclosed Choi and Johnson et al. processes. Both were novel and both had a basis for showing nonobviousness. 

FM Formaldehyde TH4 = Tetra hydrofolate DNA = Deoxyribonucleic Acid GSH Glutathione NAO+ = Nicotinomide adenosine dinucleotide SFGH = S-Formyl Glutathione hydrolase FOH = Formaldehyde Dehydrogenase... 

A new rhazinilam derivative, rhazinal (349) has been obtained from a Malayan Kopsia species [232]. The spectral data indicated that rhazinal is the S-formyl derivative of rhazinilam. Rhazinal (349) represents the first instance of a naturally occurring rhazinilam derivative which... 

R1 =—0-CH2-0CH3 2-(4-Methoxymethoxy-phenyl)-propanaP28 59% R -R2 =-(CH2)s- Formyl-cyclohexan 2S 90%... 

S. Formyl derivatives. Formic acid condenses with primary and secondary amines to yield formyl derivatives ... 

S-Formylation. Amino esters a . drochloride salt with the reagent and E... 

To a mixture of 3.2 g POCI3 and 2.8 g N-methylformanilide that had been heated briefly on the steam bath (to the formation of a deep claret color) there was added 2.3 g 5-methoxy-1,3-benzoxathiol, and steam bath heating was continued for an additional 5 min. The reaction mixture was poured into 100 ml H20, and after a few minutes stirring, the insolubles changed to a loose solid. This was collected by filtration, H20 washed and, after sucking as dry as possible, recrystallized from 30 ml boiling MeOH. This provided 1.9 g of S-formyl-S-methoxy-TO-benzoxathiol as brownish needles that melted at 119-120 °C. 

Similarly, GSH is a cofactor in the enzymatic oxidation of the toxic formaldehyde. Here, the 5-methylol—GSH adduct is oxidized by NAD, the S-formyl intermediate hydrolyzed yielding GSH and formic acid. 

Pyridine (s. a. under POClg) S-Formylation of phenols with acetic formic anhydride... 

Caspi E, Wicha J, Arunachalam T, Nelson P, Sp-itellerG (1984) Estrogen biosynthesis concerning the obligatory intermediacy of 2>S-hydroxy-10l/S-formyl androst-4-ene-3,17-dione. J Am Chem Soc 106 7282-7283... 

Me glycoside, (5 - 3 ) cyclic hemiacetal Methyl S-deoxy-S-formyl-a-D-lyxofura-noside hemiacetal [4144-96-1]... 

Amino-4.6.biB-acetaniino-phenol IS, 570. Oxim dea [N A-Mothoxy-S-formyl-phenyl)-... 

During heating and in an alkaline environnient, this compound spontaneously isomerises to S-formyl-H PteGlu. ... 

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