Methionine analogs

Kauss (39) has shown that the esterification of the carboxyl groups in the D-galacturonic acid chain takes place by a transfer of the methyl groups from S-adenosyl-L-methionine, analogous to the case in which the 4-methyl ether groups are transferred to D-glucuronic acid of hemi-cellulose (40). 

L-Cysteine and L-methionine analogs, incorporated in proteins, altering the biological properties... 

Kase H, Nakayama K. Production of O-acetyl-L-homoserine by methionine analog-resistant mutants... 

Chem. Biol, 2, 31-32 (b) Dalhoff, C., LukinaviJius, G., KlimaSauskas, S., and Weinhold, E. (2005) Synthesis of S-adenosyl-L-methionine analogs and their use for sequence-specific transalkylation of DNA by methyltransferases. Nature Pratoc., 1, 1879-1886. 

Methylmercaptopropionaldehyde is also used to make the methionine hydroxy analog CH2SCH2CH2CH(OH)COOH [583-91 -5] which is used commercially as an effective source of methionine activity (71). AH commercial syntheses of methionine and methionine hydroxy analog are based on the use of acrolein as a raw material. More than 170,000 tons of this amino acid are produced yearly (30) (see Amino acids). One method for the preparation of methionine from acrolein via 3-methyhnercaptopropionaldehyde is as follows. 

Similarly, by adding analogs of L-methionine, the methylation of C6 is inhibited, resulting in the formation of 6-demethylchlortetracycline. The analogs that may be used include D-methionine and ethionine. 

Biocatalytic access to both antipodal sulfoxides was exploited in total syntheses of bioactive compounds, which is outlined in some representative examples. Biooxidation of functionalized dialkyl sulfides was utilized in the direct synthesis of both enantiomers of sulforaphane and some analogs in low to good yields and stereoselectivities (Scheme 9.27) [206]. This natural product originates from broccoli and represents a potent inducer of detoxification enzymes in mammalian metabolism it might be related to anticarcinogenic properties of plants from the cruciform family. All four possible stereoisomers of methionine (R = Me) and ethionine sulfoxides... 

The biosynthesis of two major classes of red tide toxins, saxitoxin analogs and brevetoxins, have been studied. It was shown that saxitoxin is biosynthesized from arginine, acetate, and methionine methyl group. Brevetoxins were shown to be unique polyketides, which are probably biosynthesized from dicarboxylic acids. Some details of the biosynthetic mechanism have been elucidated. 

Peroxynitrite easily oxidizes nonprotein and protein thiyl groups. In 1991, Radi et al. [102] have shown that peroxynitrite efficiently oxidizes cysteine to its disulfide form and bovine serum albumin (BSA) to some derivative of sulfenic acid supposedly via the decomposition to nitric dioxide and hydroxyl radicals. Pryor et al. [124] suggested that the oxidation of methionine and its analog 2-keto-4-thiomethylbutanic acid occurred by two competing mechanisms, namely, the second-order reaction of sulfide formation and the one-electron... 

Once the azacytosine analogs are incorporated into the DNA, they are also subjed to a covalent addition of the thiol group of the DNMT and an adduct (la) similar to (I) in Figure 8.5 is formed. This addud (la) in most cases also reacts with S-adenosyl methionine (II) to a methylated addud (Ilia). But due to the absence of an a-proton the enzyme carmot be liberated by elimination and remains trapped to DNA (Figure 8.8). 

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