Glyceraldehyde derivatives

Addition of the lithium salt of tris(triphenylthio)methane to the D-glyceraldehyde-derived nitroolefin 80 resulted in a stereoselective Michael addition leading to adduct 81, which was then converted into the novel... 

The substrate-controlled diastereoselective addition of lithiated alkoxyallenes to chiral nitrones such as 123, 125 and 126 (Scheme 8.32) furnish allenylhydroxyl-amines as unstable products, which immediately cydize to give enantiopure mono-orbicyclic 1,2-oxazines (Eqs 8.25 and 8.26) [72, 76]. Starting with (R)-glyceraldehyde-derived nitrone 123, cydization products 124 were formed with excellent syn selectivity in tetrahydrofuran as solvent, whereas precomplexation of nitrone 123 with... 

With glyceraldehyde-derived enones and enoates, it has been found that addition of aryl or alkenyl copper reagents is almost independent of the enone geometry [24, 25]. In agreement with the modified Felkin-Anh model, Z enoates usually provide high levels of anti selectivity (Scheme 6.11). Hence, the Z derivative 64 reacted with complete stereochemical control, whereas the -enoate 64 gave a lower selectivity of 4 1 in favor of the anti-conjugate adduct [25]. 

Recently, two more stereoselective cases of bromine-lithium exchange reactions have been observed. Both the glyceraldehyde-derived bromoalkene 45 and lactaldehyde-derived 47 yield the -configurated lithium carbenoids 46 and 48, respectively, when treated with... 

A different type of heterocyclic compound, 1,2-oxazines 201, are accessible from the addition of 1-lithio-l-methoxyallene 183 to isopropylidene glyceraldehyde-derived nitrone 200. The predominant formation of the yw-configurated product 201 (syn anti > 98 2) results. Nevertheless, the stereochemical outcome can be reversed by a precomplexation of the nitrone 200 with diethyl aluminum chloride (equation 79)"". ... 

Yamagishi, S., Nakamura, K., Inoue, H., Kikushi, S., and Takeuchi, M. (2005). Serum and cerebrospinal fluid levels of glyceraldehyde-derived advanced glycation end products (ages) may be a promising biomarker for early detection of Alzheimer s disease. Med. Hypotheses 64,1205-1207. 

Another method for the preparation of 2-desoxy-D-ribose, using 2,3-isopropylidene-D-glyceraldehyde as an initial material has been outlined briefly by Overend and Stacey.106 The glyceraldehyde derivative was condensed with acetaldehyde in the presence of anhydrous potassium... 

In a similar fashion, diastereoselective addition of the vinylcuprate 103 to the glyceraldehyde-derived enone 102 was used for the construction of the precursor 104 of iso[7]-levuglandin D2.92 Besides enones and enoates, heteroatom-substituted nitroolefins and a,/3-unsaturated phosphine oxides also participate in diastereoselective copper-mediated 1,4-addition reactions.93,93 1,938... 

Intermolecular [3+2] 1,3-dipolar cycloaddition of a D-glyceraldehyde-derived nitrile oxide to the 4,5-double bond of 2-methylfuran gave a 60 40 diastereomeric ratio of the two furoisozaxoline isomers. This chemistry was employed in the synthesis of L-furanomycin <2005EJ03450>. As depicted in Scheme 43, an intramolecular cycloaddition of a furan with a carbonyl ylide dipole proceeded under rhodium-catalyzed microwave-promoted conditions to provide the cycloadduct in a modest yield <20040L3241>. 

Kinetic Resolution by Hydrolysis. Until very recently, kinetic resolution of racemic alcohols as ester derivatives was by far the most common type of asymmetric transformations involving lipases. There are number of examples involving acyclic secondary alcohols, such as the glyceraldehyde derivative in eq 1 and various related alkyl- and aryloxy substituted chloride and tosylate glycerol derivatives. - ... 

An alternative method (Scheme 13.29) for the homologation of the D-glyceraldehyde derivative (7 )-24 to derivatives of D-erythrose 60 and D-threose 61 was proposed by Kusakabe and Sato [68]. Reaction of (7 )-24 with appropriate l-(trimethylsilyl)vinyl-copper reagents lead to either anti or... 

Both exo- and endo-brevicomin vide infra), in optically active form, have been synthesized by elaboration of a-alkoxy aldehyde (201). Condensation of the 1-trimethylsilylvinylcopper reagent (198) with the ( )-glyceraldehyde derivative (199) gave syn product (200) in >85% yield with over 98% dia-stereoselectivity (Scheme 36). Hydroxy protection, hydrolysis and periodate cleavage of the vtc-diol converted (200) to aldehyde (201) in 50-65% overall yields for the two steps. 

Cativiela, C., Diaz-de-Villegas, M. D., Galvez, J. A., Garcia, J. L. Diastereoselective Strecker reaction of D-glyceraldehyde derivatives. A novel route to (2S,3S)- and (2R,3S)-2-amino-3,4-dihydroxybutyric acid. Tetrahedron 1996, 52, 9563-9574. 

Other aldose/ketose isomerases with different substrate specificity have been cloned and overexpressedl86, including Fuc isomerase (Fuc I, EC 5.3.1.3) and Rha isomerase (Rha I, EC 5.3.1.14). Fuc isomerase, in combination with Fuc 1-P aldolase or Rha 1-P aldolase, has been used to prepare L-glucose, L-galactose, L-fucose, and derivatives from the corresponding L-glyceraldehyde derivatives and DHAP 87. ... 

The bulkiness and type of the protecting group of the diol moiety of D-glyceraldehyde derivatives 7-9 influences, as expected, the stereochemical outcome of the [4 + 2] cycloaddition and the highest diastereoselectivity is achieved for the most sterically demanding protective group in aldehyde 821. For the special case involving the di-0-benzyl derivative see Section 1.6.1.1.3.2.2. 

The (A)-glyceraldehyde derivative 61 has also been nsed for the synthesis of bengamide E (3) (Scheme 6) Silylation of enoate 61 followed by redaction with DIBAL-H afforded 62, which nnderwent Sharpless epoxidation followed by iodination of the primary hydroxyl gronp to afford 63. Reaction of 63 with rerr-bntyllithinm and dimethyl snlfate and snbseqnent in situ methylation gave the methyl ether 64 in a 95 5 mixtnre of anti and syn prodncts. Ozonolysis of 64 followed by hydrolysis of the silyl ether gave 53, which nnder similar seqnence of reactions nsed in the former scheme gave 3. 

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