Allyl glucoside

Allyl isothiocyanate, CHj CH. CH N C S, also known as artificial mustard oil, is the principal constituent of natural oil of mustard. This body results from the hydrolysis of the glucoside sinigrin under the influence of the ferment myrosin, according to the equation—... 

Allylic methyl group hydroxylation and oxidation to carboxylic acid Beauveria bassiana) Allylic methyl group hydroxylation and lactate ester formation glucosidation Cunninghamella echinulata)... 

The methyl and ethyl ethers of the dianhydrides have properties which may make them useful as plasticizers. 2,5-Diallyl-dianhydro-sorbitol (XVII) and 2,5-diallyl-dianhydro-mannitol (XVIII) and the corresponding methallyl derivatives polymerize to resinous materials on being heated in oxygen.The allyl derivatives polymerize about five times as fast as the methallyl derivatives, to give products somewhat similar to that obtained by Nichols and Yanovsky by the polymerization of methyl tetraallyl-a-n-glucoside. 

Sulfoxides occur widely in small concentrations in plant and animal tissues, eg, allyl vinyl sulfoxide [81898-53-5] in garlic oil and 2,2 -sulfinylbisethanol [3085-45-8] as fatty esters in the adrenal cortex (1,2). Homologous methylsulfinylalkyl isothiocyanates, which are represented by the formula CH3SO(CH2)kNCS, where n = 3 [37791-20-1], 4 [4478-93-7], 5 [646-23-1], 8 [75272-81-0], 9 [39036-83-4], or 10 [39036-84-5], have been isolated from a number of mustard oils in which they occur as glucosides (3). Two methylsulfinyl amino acids have also been reported methionine sulfoxide [454-41-1] from cockroaches and the sulfoxide of JT-methylcysteine, 3-(methylsulfinyl)alanine [4740-94-7]. The latter is the dominant sulfur-containing amino acid in turnips and may account in part for their characteristic odor (4). 

We took advantage of this observation in order to effect selective debenzylations, once an allylic appendage is attached to the sugar. For example, when the polybenzylated allyl-C-glucopyranoside 7 (10) is treated with iodine in THF at 0 °C, the bicyclic compound 8 is obtained (85 15 in favor to the 2 R isomer), which upon treatment with zinc and acetic acid undergoes a reductive elimination affording the C-glucoside 9 selectively deprotected at C-2. (11)... 

Examination of specific carbohydrate-protein interactions can be accomplished with C-glycosides (Scheme 1). A series of C-glucosides and C-mannosides, such as 1, were employed to study the binding differences between mannose and glucose specific lectins (9). C-Mannoside derivatives (3-5) were synthesized from C-allyl derivative 2 and used to block cell-surface lectins thereby inhibiting bacterial adhesion (JO). The primary amine of 4 was functionalized with biotin to target proteins to the bacterial cell surface. 

Allyl iso-thio-cyanate is found in nature as a glucoside constituent of mustard seed. It is known, therefore, as mustard oiL It is a liquid with a sharp odor and with a boiling point of 150.7 . The proof that it is iso-thio-cyanate is its conversion into allyl-amine, CH2 = CH—CH2NH2. 

Regio- and stereo-controlled iodocyclizations of allylic trichloroacetimidates provide a route to cw-hydroxyamino sugar from hexenopyranosides. For example, conversion of the hydroxyl of compound 117 into the trichloroacetimidate 118 followed by IDCP-mediated intramolecular cyclization, gives iodo-oxazoline derivative 119, which is reduced (Bu3SnH) and hydrolyzed (pyridine, TsOH) to afford IV-acetyldaunosamine methyl glucoside 120 (O Scheme 57) [95]. 

As shown in O Table 2, this procedure enables the synthesis of a variety of 8-C-glucosides and -C-galactosides with substituents such as alkyl, allyl, vinyl, alkynyl, propargyl, aromatic, heteroaromatic [20], and acetyl groups. 

The stereoselective formation of allylic alcohol 322 (15 1 ratio) by the CrCl2/NiCl2-mediat-ed coupling reaction [134] of vinyl iodide 320, generated from C-allenyl glucoside 319, and aldehyde 321, available in six steps from L-xylose, is the key assembling step in the synthesis of methyl C-isomaltoside 20 [135] (O Scheme 68). 

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