Aldehydes from activated methyl groups

The most popular lands of the diols for asymmetric synthesis are bis-secondary diols that have a C2 axis of symmetry [212]. The presence of the symmetry axis avoids the formation of diastereoisomeric esters or acetals [213], (1R, 27 )-Cyclohexanediol 1.34 (n = 1) has been used as an auxiliary in asymmetric cyclopropanation [214] and (IS, 2S)-cycloheptanediol 1.34 (n = 2) in 1,4-addition of cuprates[157], Dioxolane derivatives of 1.34 have been used for asymmetric P-ketoester alkylations [215] and cuprate 1,4-additions [216]. Linear 1,2-diols 1.35 (R = Me, i-Pr, c-CgH j, Ph) and functionalized 1,2-diols 1.36 (Y = COOalkyl, CONR 2, CH2OR ) are readily available from optically active tartaric acids 1.36 (Y = COOH). Acetals derived from these diols are valuable reagents m asymmetric synthesis [173, 213, 217], as the related 1,3-diols 1.37. Acetals of 1,3-butanediol 137 (R = Me, R = H) have also been used. When these acetals are formed from aldehydes under thermodynamic conditions, one 1,3-di-oxane stereoisomer often predominates. In this favored isomer, the substituent from the aldehyde and the methyl group from 1.37 are both in equatorial orientar... 

In contrast to the large variety of aromatic, olefinic, and aliphatic aldehydes which can be used as donor substrates, wild-type BFD does not tolerate a modification of the methyl group of acetaldehyde in the case of aliphatic acceptor aldehydes. Apart from acetaldehyde, BFD shows activity with aromatic and heteroaromatic aldehydes as the acceptor substrate, forming enantiomerically pure (R)-benzoin and derivatives (Table 2.2.7.3, entries 6-8) [55]. 

To demonstrate that optically active aldehydes from formylation of the methyl groups of optically active olefins can be obtained as main reaction products with good optical yields, we have studied the hydroformylation of ( + )(S)-2,2,5-trimethyl-3-heptene. None of the methyl groups of the tertiary butyl group were carbonylated. Primarily the reaction product was from carbonylation of the other two methyl groups present in the molecule (Table 1). (S)-3-Ethyl-6,6-dimethylheptanal... 

The reactivity of these methyl groups is normally enhanced by nitrogen atom quaternization. Benzotroponopyridinium salt 505 with two molecules of azulene aldehyde condenses to afford blue-black bis(azulenylvinyl) dye 506 (Amax 536 nm 62ZC369). Furthermore, oxazolium salt 507 condenses with activated benzothiazolium salt 508 (Scheme 134) to form unsymmetri-cal trimethine cyanine 509 (63UP1). (Dyes 512a,b arise from methylthio exchange Section IV,A,5,e.)... 

Alkyl substituents in aromatic azoloazines are reactive towards electrophilic reagents in basic media. Basic reagents readily abstract protons from such alkyl groups yielding resonance stabilized carbanions. Thus, treatment of the methyl derivatives (243) with aldehydes gives the alkenes (245) (Scheme 21) <84H(22)174i). Ready formation of the resonance stabilized anions (244) is behind the activity of the methyl group. 

Nitro alcohols ate usually isolated (method 102) but are sometimes dehydrated directly to olefinic nitro compounds as in the preparation of co-nitro-2-vinylthiophene from nitromethane, thiophenecarboxaldehyde, and sodium hydroxide (78% yield). Many substituted /3-nitrostyrenes have been obtained by condensation of nitromethane or nitroethane with substituted benzaldehydes. A methyl group on the benzene ring is sufficiently activated by nitro groups in the orlio or para position to cause condensation with aldehydes. A series of nitrostilbenes has been made in this way from substituted benzaldehydes. ... 

One of the earliest syntheses of a chiral compound from a carbohydrate was reported by Wolfrom, Lemieux and Olin, who described the preparation of optically active L-alanine from D-glucosamine [17]. This transformation was devised to establish the strucmre of alanine from the known D-glucosamine. Only a few functional group manipulations were needed in this synthesis, such as elaboration of the aldehyde group into the methyl group of alanine through the corresponding dithioacetal. Excision of three carbon atoms was also required (Scheme 11.1). 

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