205251-18-9

Upstream product

• 98147-48-9 2-isopropyl-5-methylcyclohexyl 4-methylbenzenesulfinate 
• 1517-82-4 (-)-menthyl p-toluenesulfinate 
• 104480-60-6 (3,3-dimethylbut-1-yn-1-yl)magnesium bromide 
• 917-92-0 3,3-Dimethylbut-1-yne 
• 5804-85-3 diethylaluminium cyanide 
• 205251-14-5 (S)-3,3-dimethyl-1-butynyl p-tolyl sulfoxide 
• 7677-24-9 trimethylsilyl cyanide 

Downstream Products

• 373365-55-0 (3S,4S)-3-tert-butyl-4-[(R)-p-tolylsulfinyl]-4,5-dihydro-3H-pyrazole-3-carbonitrile 
• 373365-58-3 (3S,4S,5S)-3-tert-butyl-5-methyl-4-[(R)-p-tolylsulfinyl]-4,5-dihydro-3H-pyrazole-3-carbonitrile 
• 1283760-99-5 ethyl [1S,2R,3S,10bR,(S)R]-1-tert-butyl-1-cyano-2-(p-tolylsulfinyl)-1,2,3,10b-tetrahydropyrrolo[2,1-a]isoquinoline-3-carboxylate 

Relevant academic research and scientific papers

(Z)-3-p-tolylsulfinylacrylonitriles as chiral dipolarophiles: Reactions with diazoalkanes

(figure presented) The dipolarophilic reactivity of enantiopure (Z)-3-p-tolylsulfinylacrylonitriles (1) has been evaluated with diazoalkanes. 3-Cyanopyrazoles are obtained when R = H, but with R = alkyl (Bn, n-Bu, and t-Bu) only one cycloadduct (4 or 5) is formed in high yield under mild conditions, therefore evidencing a complete control of the regioselectivity and the endolexo and π-facial selectivities. These reactions are a new straightforward entry to the synthesis of pyrazolines and related structures and reveal the excellent dipolarophilic features of (Z)-sulfinylacrylonitriles.

Synthesis and Dienophilic Behavior of Enantiomerically Pure (Z)-3-p-Tolylsulfinylacrylonitriles

The syntheses of enantiomerically pure (Z)-3-p-tolylsulfinylacrylonitrile (1b) and its 2-n-butyl (1a), 2-tert-butyl (1c), and 2-benzyl (1d) derivatives, by stereoselective hydrocyanation with Et2AlCN of their corresponding alkynylsulfoxides, are described. Asymmetric Diels-Alder reactions of these dienophiles with cyclopentadiene are also reported, the most significant finding being their total π-facial diastereoselectivity, controlled by the sulfur configuration, which can be readily inverted by using BF3 as a catalyst. The endo selectivity is very high for 1b under thermal and catalytic (ZnBr2) conditions and complete in the presence of BF3, whereas 1a and 1d only exhibit a complete endo selectivity in the presence of BF3.