Alkenes sugars

Rearrangement reaction, 138 Reducing sugar, 992 Reduction, 229. 348 acid chlorides, 804 aldehydes, 609-610. 709 aldoses, 992 alkene, 229-232 alkyne, 268-270 amides, 815-816 arenediazonium salt, 943 aromatic compounds and, 579-580... 

Enantioselective epoxidation of unfunctionalized alkenes was until recently limited to certain ds-alkenes, but most types of alkenes can now be successfully epoxi-dized with sugar-derived dioxiranes (see Section 9.1.1.1) [2]. Selective monoepox-idation of dienes has thus become a fast route to vinylepoxides. Functionalized dienes, such as dienones, can be epoxidized with excellent enantioselectivities (see Section 9.1.2). 

Triazoline imino sugar derivatives 297 that are prospective glycosidase inhibitors have been prepared as single diastereomers in high yield via an lAOC reaction of in situ generated azido alkene 296 (Eq. 32) [78]. m-CPBA oxidation of the dithioacetal groups in the 0-acetylated 5-azido-5-deoxydibenzyl dithio-acetal of o-xylose or D-ribose 294 to the bis-sulfone 295, followed by loss of HOAc between C-1 and C-2 provided the lAOC precursor 296. 

Several alkenes occur naturally in living organisms. Some of these alkenes act as hormones and control biological functions. Plants produce ethene as a hormone to stimulate flower and seed production and to ripen fruits. Ethene stimulates enzymes in the plants to convert starch and acids of unripe fruit into sugars. The enzymes also soften fruit by breaking down pectin in cell walls. 

The conversion of nitroalkanes to ketoximes can be achieved by the reduction with Zn in acetic acid,112 or Fe in acetic acid.113 Nitroalkenes are direcdy reduced into saturated ketoximes by these reagents, which are precursors for ketones (see Section 6.1.4 Nef reaction). Reduction of 3-O-ace-ty lated sugar 1 -nitro-1 -alkenes with Zn in acetic acid gives the corresponding 2,3-unsaturated sugar oximes in high yield, which is a versatile route to 2,3-unsaturated sugar derivatives (Eq. 6.58).114... 

T. K. M. Shing, W. F. Wong, H. M. Cheng, W. S. Kwok, and K. H. So, Intramolecular nitrile oxide-alkene cycloaddition of sugar derivatives with unmasked hydroxyl group(s), Org. Lett., 9 (2007) 753-756. 

However, most asymmetric 1,3-dipolar cycloaddition reactions of nitrile oxides with alkenes are carried out without Lewis acids as catalysts using either chiral alkenes or chiral auxiliary compounds (with achiral alkenes). Diverse chiral alkenes are in use, such as camphor-derived chiral N-acryloylhydrazide (195), C2-symmetric l,3-diacryloyl-2,2-dimethyl-4,5-diphenylimidazolidine, chiral 3-acryloyl-2,2-dimethyl-4-phenyloxazolidine (196, 197), sugar-based ethenyl ethers (198), acrylic esters (199, 200), C-bonded vinyl-substituted sugar (201), chirally modified vinylboronic ester derived from D-( + )-mannitol (202), (l/ )-menthyl vinyl ether (203), chiral derivatives of vinylacetic acid (204), ( )-l-ethoxy-3-fluoroalkyl-3-hydroxy-4-(4-methylphenylsulfinyl)but-1 -enes (205), enantiopure Y-oxygenated-a,P-unsaturated phenyl sulfones (206), chiral (a-oxyallyl)silanes (207), and (S )-but-3-ene-1,2-diol derivatives (208). As a chiral auxiliary, diisopropyl (i ,i )-tartrate (209, 210) has been very popular. 

Methyl 3,4,5,6-tetra-0-acetyl-2-deoxy-2-diazo-D-arabino-hexonate (84) has been irradiated in methanol and in 2-propanol.177 In methanol, the only photoproduct is the enol acetate 85 however, irradiation in 2-propanol results in formation of minor proportions (6%) of 85 and the alkene 86 (7%), but the major product is the deoxy sugar 87 (61%). The difference in reactivity of 84 in these two solvents is probably a reflection of the difference in the ability of methanol and 2-propanol to function as hydrogen donors when reacting with a carbene (see Scheme 31). In methanol, a 1,2-hydrogen atom shift to the divalent... 

SCHEME 7. Sugar-derived ketones as catalysts for asymmetric alkene epoxidation... 

In our early work, we attempted the alkylation of the amine 81 with various carbohydrate triflates, namely 82-84 [57]. Somewhat disappointingly, the main products isolated were the alkenes, e.g. 85 and 86. Only a small amount of the desired N-linked carbasugar, e. g. 87 was ever obtained. At one stage we attempted an alkylation of the amine 81 with the triflate 82 and with the triflate 84 in the presence of potassium carbonate to our surprise, carbamates were formed, 88 and 89 These two carbamates have subsequently been deprotected to give the methyl -o-glucoside 90 and the free sugar 91, interesting candidates for enzyme inhibition studies [57]. 

Some additional examples, where the stereochemical outcome of the cycloaddition to chiral alkenes has been explained in terms of the Honk—Jager model, should also be mentioned. The diastereomer ratio found in the reaction of y-oxy-a,p-unsamrated sulfones (166), with Morita-Baylis-Hillman adducts [i.e., ot-(a -hydro-xyalkyl)-acrylates (167)] (Scheme 6.27), with dispiroketal-protected 3-butene-l,2-diol (168), and with a,p-unsamrated carbonyl sugar and sugar nitroolefin (169) derivatives, all agree well with this model. 

Of the many substituted and functionalized alkenes that have been combined with diazo dipoles to give A -pyrazolines or products derived from them (i.e., A -pyrazolines, pyrazoles, cyclopropanes), only a selection will be mentioned. These include ot-alkylidene-cycloalkanones (62), -flavanones, -thioflavanones, -chroma-nones, and thiochromanones (63,64) a-arylidene-indanones and -indolones (65) diarylideneacetones (66) l-benzopyran-2(77)-ones (coumarins) (67,68) 4-nitro-1,2-oxazoles (69) 2-alkylidene-2-cyanoacetates (70) dimethyl 2,3-dicyanofuma-rate (71) tetracyanoethylene (72) tetraethyl ethylenetetracarboxylate (72) 1,4-quinones (35,73-75) 2-X-l,l,l-trifluoro-2-propene [X = Br, (76), SPh, SOPh, S02Ph (77)] nitroalkenes (78) including sugar nitroalkenes (79) 1-diethoxyphos-phoryl-1-alkenyl-sulfoxides (80) methyl 2-(acetylamino)cinnamate and -acrylate... 

A solid-phase synthesis of furo[3,2-3]pyran derivatives utilizing highly functionalized sugar templates has been reported <2003JOC9406>. After incorporation of alkenes within the sugar template, such as compound 95, the solid support is introduced via formation of the acid amide. This immobilized system then allows a ruthenium-catalyzed ring-closing metathesis that leads to the formation of the fused oxacycles. 

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