644977-16-2Relevant academic research and scientific papers
Efficient one-pot synthesis of 1-chlorovinyl p-tolyl sulfoxides from aldehydes and ketones by the Horner-Wadsworth-Emmons reaction
Kimura, Tsutomu,Kobayashi, Gen,Ijima, Shiori,Saito, Sae,Imafuji, Aki,Satoh, Tsuyoshi
, (2017/10/27)
A variety of 2-monosubstituted and 2,2-disubstituted 1-chlorovinyl p-tolyl sulfoxides was synthesized through a one-pot procedure by the Horner-Wadsworth-Emmons reaction of carbonyl compounds with [chloro(diethoxyphosphoryl)(p-tolylsulfinyl)methyl]lithium, which was generated from diethyl chlorophosphate, chloromethyl p-tolyl sulfoxide, and lithium diisopropylamide in advance. The in situ-prepared sulfoxides were directly converted into alkynes via the sulfoxide/magnesium exchange reaction with i-PrMgCl and the subsequent Fritsch-Buttenberg-Wiechell rearrangement of the resulting magnesium alkylidene carbenoids.
A new synthesis, including asymmetric synthesis, of spiro[4.n]alkenones from three components: Cyclic ketones, chloromethyl p-tolyl sulfoxide, and acetonitrile; and a formal total synthesis of racemic acorone
Satoh, Tsuyoshi,Kawashima, Tadashi,Takahashi, Satoru,Sakai, Ken
, p. 9599 - 9607 (2007/10/03)
1-Chlorovinyl p-tolyl sulfoxides were synthesized from several kinds of cyclic ketones and chloromethyl p-tolyl sulfoxide in good yields. Treatment of the 1-chlorovinyl p-tolyl sulfoxides with cyanomethyllithium at -78°C to room temperature gave spirocyclic enaminonitriles in high yields. Acidic treatment of the enaminonitriles afforded spiro[4.n]alkenones in good yields. By using an unsymmetrical cyclic ketone, α-tetralone, and optically active chloromethyl p-tolyl sulfoxide, this procedure afforded enantiomerically pure spiro[4.5]decenone in good yield with excellent asymmetric induction from the sulfoxide chiral center. By using this method a formal total synthesis of a racemic spirocyclic sesquiterpene, acorone, was realized.
