Glyoxylic acid derivatives

Figure 10.4. Preparation of glyoxylic acid derived imines [130].

The Morita-Baylis-Hillman reaction of chiral glyoxylic acid derivatives with cyclic a,/ -unsaturated ketones proceeded under the catalytic influence of dimethyl sulfide in the presence of titanium tetrachloride [27]. The adducts were obtained with high diastereomeric excess (>95% de) and typical yields around 80%. 

Imines derived from glyoxylic acid derivatives successfully lead to 3-lactams which are potential precursors of various antibiotics (equation 29). Conjugated imines have also been used in this context they give exclusively [2 -i- 2] cycloadducts with azido-, phthalimido-, phenoxy- and vinyl-ketene precursors (equations 30 and 31). However, [4 -i- 2] adducts are the only observed products with haloketene precursors (equation 32). - ... 

Highly diastereoselective nitroaldol reactions <2003TL8681> and Lewis acid-catalyzed reactions with furan derivatives <2000PAG1589> on enantiopure glyoxylic acid derivative 586 (R = H, X = 0) were performed. 

Glyoxylic acid derivatives in asymmetric synthesis (N-glyoxyl-(2R)-bornane-10,2-sultam as a key compound) 00PAC1589. 

Evans SM, Huang B-S, Feng D, et al. Probing the 5-HTs receptor site using novel indole-3-glyoxylic acid derivatives. Med Chem Res 1993 3 386-406. 

The glyoxylic acid derivatives 53 (Fig. 18.10) were discovered by Bayer in 1994 as a new class of Oomycete fungicides by derivatization of advanced research project compounds with broad fungicidal activity [6]. 

Fig. 18.11. Examples of glyoxylic acid derivatives displaying specific activity against Oomycetes.

Chiral glyoxylic acid derivatives, i.e. (— )-8-phenylmenthyl glyoxylate, imdergoes an MBH reaction with cyclic a,p-unsaturated ketones under the... 

Other apphcations of this type of reaction include the formation of glyoxylate esters 1272 and 1276, which are useful intermediates for the manufacture of pharmaceuticals and in the synthesis of glyoxylic acid derivatives [955-957]. 

Glyoxylic acid-derived iminolactone 30 has also been used in a diastereoselective addition reaction to form 31 (Equation 3) [47]. Fukuyama attributed the selectivity of this reaction to attack of the nucleophile from the less hindered face of the iminium ion derived from 30. 

A convenient method of synthesis of pharmacologically attractive imidazoquinoxaline derivatives 75a-g has been described (DeMoliner and Hulme 2012b). The method involves the three-component reaction of A-Boc-o-phenylenediamines 76a-d with glyoxylic acid derivatives, namely, with ethyl glyoxylate (see Sect. 4.4) and benzylglyoxylamide 77, with the participation of tosylmethyl isocyanides. The reaction is carried out under microwave irradiation [the Van Leusen and Van Leusen modification (2012)]. It is likely that, first, the condensation of aldehyde at the free amino group of compounds 76a-d leads to imines 78a-d, which are... 

Behr D, Brandange S, Lindstrom B (1973) Synthesis of some aryl a-diketones and aryl glyoxylic acid derivatives by acylation of electron-rich aromatics. Acta Chem Scand 27 2411-2414. doi 10.3891/acta.chem.scand.27-2411... 

ZOLLER, U., and D. Ben-Ishai Amidoalkylation of Mercaptans with Glyoxylic Acid Derivatives. Tetrahedron 31, 863 (1975). 

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