Inorganic Derivatives

Arsenic derivatives of thiosugars and selenosugars, e.g. compounds (10) and (11), have been prepared from the corresponding thiol and selenol by treatment with dimethylarsenic chloride.  

The synthesis of 5-alkylphosphinyl-5-deoxy-D-xylopyranose and its derivatives has been noted in Chapter 12.  

Phosphorylation of protected D-glucopyranose and D-galactopyranose with dioxaphosphorinane or 6-methyldioxaphosphorinane gave the corresponding glycosyl phosphorus derivatives (1). Similarly prepared were the phosphono-diamidite and benzyl phosphonoamidite derivatives (2) and (3). Treatment of 

Triphenyltin lithium has been used to open the oxiran rings of methyl 2,3-anhydro-4,6-0-benzylidene-a-D-allo- and -mannopyranosides to give the tin-bonded altrosides (10) and (11) in 75 and 94% yield respectively. A 43% yield of the C-6 bonded tin derivative (12) was obtained by using the reagent to displace the corresponding tosylate. The n.m.r. of these products is reported in Chapter 20.  

A comparative study of the chelation of 2-deoxy-D-ribose with boric, germanic, telluric, and arsenious acids using potentiometry has shown that only 1 1 complexes are formed. Values of the chelation constants were compared with those of the pentoses. A similar study on mannitol and glucose with boric acid demonstrated that the former was about 740 times more effective a complexant than glucose, but that the conclusions were complicated by the degree of association of boric acid in solution. Reactions at the anomeric centre of mannofuranose have been carried out by means of the 2,3 5,6-ethylboronate (1) formed by treatment of D-mannose with limited triethyl boroxine. By the same means D-lyxose gave the 2,3-blocked lyxofuranose (2) also useful for 

The C n.m.r. of aldoses complexed to molybdate shows that ribose, talose, and allose behave as tridentate donors using hydroxy-groups at positions 2, 3, 

Derivatives of carbohydrates that have been used to complex with rhodium catalysts to promote asymmetric hydrogenation include the phosphorus derivatives (6) and (7)/ and (8) (12) synthesized by esterification of the hydroxy-compounds with the appropriate phosphonyl chloride. Treatment of 7r-allyl-palladium chloride with the phosphite ester (13) gave a complex that was an enantioselective catalyst for hydrogenation of unsaturated acids and esters.  

The H and n.m.r. of the Ca complex of A -glycolylneuraminic acid at pH 7 showed that a 1 1 complex is formed. Analysis of electric field shifts gave the approximate position of the ion shown in formula (14). The interactions of Na , Ca , and La with methyl glycofuranosides in methanol have been studied by measurement of the rate of acid-catalysed methanolysis in the presence of chlorides. Rates decreased with increasing ionic charge. The conclusion was reached that steric requirements for complex formation with metal ions differ even when the ionic radius is approximately the same and that the main factor is charge, to which is related the ability to deform the furanoside.  

An extensive range of ferrocene-sugar derivatives has been reported and studied by H n.m.r.  

The sugar phosphines (431) and (432) have been prepared and used as ligands for Wilkinson s catalysts in the asymmetric hydrogenation of prochiral olefins.  

Yoshida, and M. Sato, Nippon Kagaku Kaishi, 1976,1652 (Chem. Abs 1977,86,90 155g). M. Yamashita, Y. Nakatsukasa, M. Yoshikane, H. Yoshida, T. Ogata, and S. Inokawa, Carbohydrate 

An analogous sequence of reactions with methyl 2,3-dideoxy-(lS)-pentopyranosid-4-ulose 4-(toluene-p-sulphonylhydrazone) (434) afforded l,5-di-0-acetyl-2,3,4-trideoxy-4-C-(phenylphosphinyl)-DL-gfiycero-pentofuranose (435). The Abramov reaction of 2,3 5,6-di-O-isopropylidene-a-D-mannofuranose with dimethyl phosphite yielded the oxaphosphorinane (436) by intramolecular transesterification. °  

C-Stannyl derivatives of sugars [e.g. (437) and (438)] have been prepared by either the displacement of primary tosylates or the reaction of suitably protected epoxides with triphenyltin lithium in anhydrous 

The methoxymercuration of 4,6-0-benzylidene-D-allal yielded isomeric acetoxy-mercurial adducts having the -D-allo (439) and a-D-altro (440) configurations. Demercuration of (439) with sodium borohydride gave methyl 4,6-0-benzylidene-2-deoxy-P-D-ri6o-hexopyranoside (72%), the ot,p-unsaturated aldehyde (441) (8.3 %), and a trace of the original glycal, while demercuration of (440) gave methyl 4,6-0-benzylidene-2-deoxy-a-D-r/6o-hexopyranoside (40%), (442) (23.5%), and traces of other products. 

The and C- Hg couplings in specifically mercurated sugars are referred to in Chapter 23. 

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Derivatives. The nonmetaHic inorganic derivatives of fluorosulfuric acid are generally made indirectly, although complex fluorosulfates of the Group 15 (V) elements and of xenon can be made directly (85,86), as can the NO" and NO" 2 salts (26,27). 

C.B. Colburn, Nitrogen Fluorides and their Inorganic Derivatives in M. Stacey et al, eds Advances in Fluorine Chemistry 3, Butter-worths, London (1963), 92 12) E.A. Lawton... 

Peroxides, Inorganic. The inorganic derivatives of hydrogen peroxide. These compds are described by a general formula, viz, E+202,... 

Structure and bonding in inorganic derivatives of (l-diketones. D. W. Thompson, Struct. Bonding (Berlin), 1971,9,27-47 (69). 

Structural and bonding aspects in phosphorus chemistry — inorganic derivatives of oxohalogeno phosphoric acids. K. Dehnicke and A. F. Shihada, Struct. Bonding (Berlin), 1976, 28, 52-82 (119). 

Dechnicke K, Shihada A-F (1976) Structural and Bonding Aspects in Phosphorus Chemistry-Inorganic Derivates of Oxohalogeno Phosphoric Acids. 28 51-82 Denning RG (1992) Electronic Structure and Bonding in Actinyl Ions. 79 215-276 Dhubhghaill OMN, Sadler PJ (1991) The Structure and Reactivity of Arsenic Compounds. 

Thompson DW (1971) Structure and Bonding in Inorganic Derivatives of /1-Diketones. 9 ... 

C. H. van Dyke Prep. Inorg. React. Inorganic derivatives of germane 76 Pp. 215-218 germyl-transition... 

Table 2. Inorganic derivates of dichlorophosphoric acid, arranged in the order of their structural types...

Structural and Bonding Aspects in Phosphorus Chemistry-Inorganic Derivates... 

Many compounds of both organic and inorganic derivation, which contain the azide function, are unstable or explosive under appropriate conditions of initiation, not all have been given entries. The large number of compounds having entries has been subdivided for convenience on the basis of structure. 

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