Synthesis from D-mannose

3 Synthesis fromo-arabinose (+)-Prenssin (1) was also synthesized from 2,3,5-tri- 

De Armas, R Garcia-TeUado, E Marrero-TeUado, J.J. Robles, J. Tetrahedron Lett. 39 (1998) 131. 

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Swainsonine is a trihydroxylated bicyclic indolizidine alkaloid with four chiral centres, whose relative stereochemistry was determined by X-ray crystallographic analysis and the absolute configuration was deduced on the basis of biosynthetic and asymmetric induction studies, and then confirmed by an enantiospecific synthesis from D-mannose [2a]. 

Other complementary methodologies include the preparation of substituted cyclopropanes from glycals using rhodium acetate carbenoid additions [65,66]. Additionally, acid catalyzed cyclopropane opening reactions in alcoholic solutions afford the 2-C-branched-glycosides. These combined reactions were used to prepare a key intermediate in marine diterpene norrisolide synthesis from D-mannose [67]. 

D-Ribonolactone is a convenient source of chiral cyclopentenones, acyclic structures, and oxacyclic systems, useful intermediates for the synthesis of biologically important molecules. Cyclopentenones derived from ribono-lactone have been employed for the synthesis of prostanoids and carbocyclic nucleosides. The cyclopentenone 280 was synthesized (265) from 2,3-0-cyclohexylidene-D-ribono-1,4-lactone (16b) by a threestep synthesis that involves successive periodate oxidation, glycosylation of the lactol with 2-propanol to give 279, and treatment of 279 with lithium dimethyl methyl-phosphonate. The enantiomer of 280 was prepared from D-mannose by converting it to the corresponding lactone, which was selectively protected at HO-2, HO-3 by acetalization. Likewise, the isopropylidene derivative 282 was obtained (266) via the intermediate unsaturated lactone 281, prepared from 16a. Reduction of 281 with di-tert-butoxy lithium aluminum hydride, followed by mesylation, gave 282. 

Y. Chapleur, A short synthesis of 2-C-alkyl-2-deoxy sugars from D-mannose, J. Chem. Soc. Chem. Commun. p. 141 (1983). 

D. Horton and W. Weckerle, A preparative synthesis of 3-amino-2,3,6-trideoxy-L-7yxo-hexose hydrochloride from D-mannose, Carbohydr. Res. 44 221 (1975). 

The synthesis of natural products by chirality transfer from carbohydrates has been used for a total synthesis of (-)-(7S)-nonactic acid (199). The furanoid glycal (197) was prepared from D-mannose, which is the appropriate chiral precursor (Scheme 46) (80JOC4259). A [3,3]-sigmatropic rearrangement of the silylated ketene-acetal (198) led to the control of the C-2 configuration. The intermediate furanoid glycal was prepared in ten steps from the carbohydrate precursor. 

Obayashi and Schlosser [43] have briefly described syntheses of erythro-sphingo-sine and threo-sphingosine from D-mannose and D-ribono-1,4-lactone, respectively. For the synthesis of ery/Aro-sphingosine (35) D-mannose was converted into benzyl 2,3 5,6-di-O-isopropylidene-manno-furanosides and hydrolysis of the 5,6-0-iso-propylidene group followed by periodate oxidation and borohydride reduction and protection gave the methoxymethyl ether (28). This was converted into the chloride... 

M. Georges and B. Fraser-Reid, A simple, one-flask, two-step synthesis of 1,6-anhydro-/i-D-mannopyi anosc (D-mannosan) from D-mannose, Carbohydr. Res., 127 (1984)... 

Fig. 16. Enzymatic synthesis of GDP-a-D-mannose (23) from D-mannose (20) via a-D-mannose-6-phosphate (21) and ot-D-mannose-1 -phosphate (22) with in situ regeneration of ATP. A Hexokinase (EC 2.7.1.1), B Pyruvate kinase (EC 2.7.1.40), C Phosphomannomutase (EC 5.4.2.8), D GDP-Man pyrophosphorylase (EC 2.7.7.13), E inorganic pyrophosphatase (EC 3.6.1.1) [311]...

The enantioselective preparation of both optical antipodes of oxabicyclo[4.2.1]-, -[5.2.1], and -[6.2.1]alkenes was reported by Garcia-Tellado and co-workers <01EJO4423> (Scheme 51). The starting diene in these cases is derived in several steps from D-mannose use of D-xylose as starting material allows the synthesis of the opposite enantiomers. 

An asymmetric synthesis of aminocyclopentitols 134-137 has been used in the synthesis of trehazolin via free-radical cycloisomerization of enantiomerically pure, alkyne-tethered oxime ethers derived from D-mannose (Scheme 17).84 Treatment of 2,3 5,6-di-(9-isopropylidene-D-mannofuranose (128)85 with ethynylmagnesium bromide gave compound 129, which underwent sequential one-pot acid hydrolysis plus diol cleavage to give 130, oximation of which afforded the radical precursor 131, in 41% overall yield from 129. The free hydroxyl group of 131 was protected as acetate 132 and tert-butyldimethylsilyl ether 133, which were isolated as inseparable... 

I. S. de Gracia, S. Bobo, M. D. Martin-Ortega, and J. L. Chiara, A concise and highly efficient synthesis of trehazolin and trehalamine starting from D-mannose, Org. Lett., 1 (1999) 1705-1708. 

Gomez, A M, Moreno, E, Valverde, S, Lopez, J C, Stereodivergent synthesis of carbasugars from d-mannose. Syntheses of 5a-carba-alpha-D-allose, beta-L-talose, and alpha-L-gulose pentaacetates, Synlett, 891-894, 2002. 

Oishi, T, Ando, K, Chida, N, Stereoselective total synthesis of (-l-)-myriocin from D-mannose, Chem. Commun., 1932-1933, 2001. 

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