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1.2.1.1.3 Organosilicon Compounds as Biginelli Reaction Promoters

DOI: 10.1055/sos-SD-210-00013

Chebanov, V. A.; Gorobets, N. Yu.; Sedash, Yu. V.Science of Synthesis: Multicomponent Reactions, (2014141.

Organosilicon compounds are widely used as water scavengers in reactions of carbonyl compounds.[‌77‌] In 1992, Zavʼyalov and Kulikova suggested using chlorotrimethylsilane in dimethylformamide as promoter of the Biginelli reaction. The desired 3,4-dihydropyrimidin-2(1H)-one derivatives are obtained in 62–80% yields from aromatic aldehydes and in 32–37% from aliphatic aldehydes at room temperature. The procedure includes two steps: first, the β-dicarbonyl compound and the aldehyde undergo aldol condensation to give an α,β-unsaturated ketone, and then urea is introduced into the reaction mixture to react with the product of the previous step. The final products are isolated and purified by chromatography.[‌78‌] Application of chlorotrimethylsilane was further developed for the synthesis of 2-(thi)oxo-1,2,3,4-tetrahydropyrimidine-5-carboxylates (e.g., 13) of different types.[‌77‌,‌79‌] The advantage of the method is the possibility of using mono- and disubstituted ureas (Scheme 11).

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Meeeeeeeeee 88

M8 M8 M8 M Meeee (%) Mee
8-M8MM8M8 Me M M 88 [‌88‌]
Me Me M M 88 [‌88‌]
8-MeMM8M8 Me Me M 88 [‌88‌]

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Meeeee 88 Meeeeeeeeeeeee Meeeeeeeeeeeeeeeeeeeeeeee Meeeeeee Meeeeeeee Meeeeeee[‌88‌]

Meeeeeeeeee 88

M8 M8 M8 M Meeee (%) Mee
Me Me Me M 88 [‌88‌]
8-MeMM8M8 Me Me M 88 [‌88‌]
8-Me8MM8M8 Me Me M 88 [‌88‌]
8,8-(MeM)8M8M8 Me Me M 88 [‌88‌]
8-MMM8M8 Me Me M 88 [‌88‌]
8-eeeee e-Me Me M 88 [‌88‌]
eMe Me Me M 88 [‌88‌]
MM=MMMe Me Me M 88 [‌88‌]

Meeeeeeeeeee Meeeeeeee

8-Meeeeeeeeee eee 8,8-Meeeeeeeeeeee Meeee 8-Meeeee-8-(eee)eee-8,8,8,8-eeeeeeeeeeeeeeeeeeee-8-eeeeeeeeeeee 88; Meeeeee Meeeeeeee:[‌88‌]

Meeee eeeeeeeeeeee (8 eeee), eee eeeeeeee (8 eeee), eee eee eeee ee eeeeeeee (8.8–8.8 eeee) eeee eeeeee ee e 88-eM Mee eeeeeeee eeee eee eeeeeeeee ee MMM (88 eM). MMMMe (88 eeee) eee eeeee eeeeeeee ee eee eeee. Mee eeee eee eeeeeeeeee eeeeee eee eeeeeee ee eeeee ee ee ee ee eeeeeeeeee eeee eee 8 e eee eeee eeee ee eeeee ee ee eee 8–8 e. Mee eeeeeee eee eeeeee eeee M8M (88–88 eM) eee eeee ee ee ee ee eeeeeeeeee eeee eee 8 e. Mee eeeeeeeeeee eeee eeeeee eee eeeeeeeee ee eeeeeeeeee eee eeeeee eeee e eeeee eeeeee ee eMeMM. M eeeeeee 8–88% ee eee eeeeeee eeeee ee eeeeeeeee ee eee eeeeee eeeeee eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee eee eee eeeeeee eee eeeeeee eeee e eeeee eeeeee ee eMeMM ee Me8M.

Meeee 8-(8-Meeeeeeeeeeee)-8-eeeeee-8-eee-8,8,8,8-eeeeeeeeeeeeeeeeeeee-8-eeeeeeeeeee (88, M8 = 8-MeMM8M8; M8 = Me; M8 = Me; M = M); Meeeeee Meeeeeeee:[‌88‌]

M eeee ee 8-eeeeeeeeeeeeeeeeeee (888 ee, 8.8 eeee), eeee (888 ee, 8.8 eeee), eee eeeee eeeeeeeeeeee (88, M8 = Me; M8 = Me; 888 ee, 8.8 eeee) ee MeMM (8 eM) eee eeeeeee ee ee ee eee eeeeeeee ee MMMMMe (8 ee, 8 eee%) eee 88 eee (eeeeeeee ee eee eeeeeeee eee eeeeeeeee ee MMM). Mee eeeeeee eee eeee eeeeee eeee eeeeeee eee (88 e) eee eeeeeee eee 8–88 eee. Mee eeeeeeeee eeeee eee eeeeeeeee ee eeeeeeeeee eeeeeee e eeeeeeee eeeeee eeeee eeeeeee, eeeeee eeee eee-eeee M8M (88 eM), eee eeeeeeeeeeeeee (eee MeMM) ee eeeeee eee eeee eeeeeee; eeeee: 8.88 e (88%).

References


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