Sugars, branched-chain synthesis

Alkylation of enamines with epoxides or acetoxybromoalkanes provided intermediates for cyclic enol ethers (668) and branched chain sugars were obtained by enamine alkylation (669). Sodium enolates of vinylogous amides underwent carbon and nitrogen methylation (570), while vicinal endiamines formed bis-quaternary amonium salts (647). Reactions of enamines with a cyclopropenyl cation gave alkylated imonium products (57/), and 2-benzylidene-3-methylbenzothiazoline was shown to undergo enamine alkylation and acylation (572). A cyclic enamine was alkylated with methylbromoacetate and the product reduced with sodium borohydride to the key intermediate in a synthesis of the quebrachamine skeleton (57i). 

Recent progress of basic and application studies in chitin chemistry was reviewed by Kurita (2001) with emphasis on the controlled modification reactions for the preparation of chitin derivatives. The reactions discussed include hydrolysis of main chain, deacetylation, acylation, M-phthaloylation, tosylation, alkylation, Schiff base formation, reductive alkylation, 0-carboxymethylation, N-carboxyalkylation, silylation, and graft copolymerization. For conducting modification reactions in a facile and controlled manner, some soluble chitin derivatives are convenient. Among soluble precursors, N-phthaloyl chitosan is particularly useful and made possible a series of regioselective and quantitative substitutions that was otherwise difficult. One of the important achievements based on this organosoluble precursor is the synthesis of nonnatural branched polysaccharides that have sugar branches at a specific site of the linear chitin or chitosan backbone [89]. 

The general approach has been followed for the de novo synthesis of a multitude of differently substituted, unsaturated [112,113] or regiospedfically labeled sugars [102,114]. Unusual branched-chain (42), (43)) and spiro-annulated sugars (45), (46)) have been synthesized from the corresponding aldehyde precursors... 

The aqueous Heck coupling reaction was also used for the synthesis of unprotected branched-chain sugar. In the media of DMF-H2O (5 1) and the use of Pd(dba)2 and P(o-tol)3 the Heck reaction proceeded smoothly to give the coupling product with high yield (up to 84%) (Eq. 3.38).148... 

H. Santos, Construction of a branched chain at C-3 of a hexopyranoside. Synthesis of miharamycin sugar moiety analogues, Carbohydr. Res., 325 (2000) 1-15. 

The favored oxidative cleavage of a primary-secondary over a primary-tertiary vicinal diol grouping has been utilized in the synthesis of branched-chain sugar derivatives.482,483... 

A simple synthesis of the branched chain sugar, 2-C-methyl-D,L-lyxofuranoside 17 has been achieved by using the tin(ll) enolate of a I 3-dihydroxy-2-propanone derivative and methyl pyruvate (23). 

As was described for phthalan 330, the intermediate 374 has also been nsed for the EPC synthesis of branched-chain sugars 378 and 379"° and the steroid 380 in 15-70% yield, employing ketones 133 and 270, as well as 280, respectively. 

M. Nomura, S. Shuto, M. Tanaka, T. Sasaki, S. Mori, S. Shigeta, and A. Matsuda, Nucleosides and Nucleotides. 185. Synthesis and biological activities of 4 -a-C-branched-chain sugar pyrimidine nucleosides, J. Med. Chem., 42 (1999) 2901-2908. 

Five-membered lactones (y-butyrolactones) fused to carbohydrates have proven to be convenient synthons towards branched-chain sugars through opening of the lactone unit. Velaskes et al. [208] described the synthesis of y-butyrolactones... 

A pentopyranoside-fused butenolide is the key intermediate for the synthesis of the natural micotoxin patulin [226, 227]. Its synthesis involves Wittig olefination of a 3,4-di-O-protected arabinopyran-2-uloside, followed by protecting group removal and dehydration (Scheme 47). In other research, the glucopyranosid-2-uloside 190 was converted into the butenolide derivative 191 by aldol condensation with diethyl malonate and transesterification [228]. The latter was shown to be prone to autoxi-dation, leading to 192. Subsequent Michael addition with hydroxide ion, followed by decarboxylation, furnishes C-branched-chain sugar 193. 

Scheme 47 Synthesis of a 2-C-branched-chain sugar via a pyranose-fused butenolide...

Raphael and Roxburgh32 33 presented a second synthesis of DL-apiose (53) which started from 4-acetoxy-3-(acetoxymethyl)-l-ethoxy-1-butene (54). This synthesis also permitted the preparation of compound 56, a branched-chain sugar then presumed, erroneously, to be... 

Incubation of D-[U-I4C]apiose with sterile Lemma minor (duckweed) produced less than 0.01% incorporation into the cell-wall polysaccharides.75 Most of the d-[U-i4C]apiose appeared as 14C02 some remained in solution in the medium and in the duckweed plants, primarily as degradation products of D-[U-14C]apiose, but not as the branched-chain sugar.75 There is an efficient synthesis of the [U-14C]apiose moiety of cell-wall polysaccharides from D-[U-14C]glucose under similar conditions.81 Of the plant tissues tested, only L. minor contained an enzyme system able to metabolize free apiose. Carrot, lettuce, and spinach tissues are unable to metabolize the free, branched-chain sugar.75... 

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