Dithianation

The carbanions derived from thioacetals, however, are typical -synthons. Most frequently used are 1,3-dithianes and C -silylated thioethers (see p. 33f. D. Seebach, 1969, 1973 B.-T. Grobel, 1974,1977). In these derivatives the proton is removed by butyllithium in THF. 

Lithium l,3-dithian-2-ides (p. 6, 8) may be alkylated with alkyl bromides or iodides. Steric hindrance is usually of little importance and the resulting ketone can be easily liberated by hydrolysis (D. Seebach, 1969). 

After the umpolung of an aldehyde group by conversion to a l,3 dithian-2-ide anion (p. 17) it can be combined with a carbonyl group (D. Seebach, 1969, 1979 B.-T. GrO-bel, 1977 B). Analogous reagents are tosylmethyl isocyanide (TosMIC), which can be applied in the nucleophilic formylation of ketones (O.H. Oldenziel, 1974), and dichloromethyl lithium (G. KObrich, 1969 P. Blumbergs, 1972 H. Taguchi, 1973),... 

A new class of synthetic aldehyde reactions involves effectively reversing the polarity of the carbonyl group by forming a dithiane intermediate. 

Hydrolysis of tfie resulting dithiane yields a ketone. 

Oxathiane and -dithiane are formed from ethylene oxide and hydrogen sulfide at 200°C in the presence of an aluminum oxide catalyst (65). 

The possibility of activating the indole nucleus to nucleophilic substitution has been realized by formation of chromium tricarbonyl complexes. For example, the complex from TV-methylindole (215) undergoes nucleophilic substitution with 2-lithio-l,3-dithiane to give a product (216) which can be transformed into l-methylindole-7-carbaldehyde (217) (78CC1076). 

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