Choi, GM Yeon, SH Jin, JG Yoo, BR Jung, IN 2024-01-21T17:45:45Z 2024-01-21T17:45:45Z 2021-09-05 1997-11-25 0276-7333 https://pubs.kist.re.kr/handle/201004/143501 Alkyltrimethylsilane reacts with simple conjugated dienes in the presence of aluminum chloride catalyst to give stereoselective [3 + 2] cycloadducts of trans-vinylcyclopentanes in 29-72% yields at -10 degrees C. The same reactions give 1,4-allylsilylated compounds as the major products at -50 degrees C, which cyclize to the annulation products as the reaction mixture is allowed to warm to -10 degrees C. The reaction using (2-methyl-2-propenyl)trimethylsilane instead of allyltrimethylsilane does not give the annulation due to an unfavorable 1,2-silyl shift, rather, allylsilylation products. The results are consistent with an initial 1,4-allylsilylation of the conjugated diene, followed by the intramolecular cyclization of the 1,4-allylsilylated alkene to the stereoselective trans-[3 + 2] cycloadduct, via a 1,2-silyl shift. English AMER CHEMICAL SOC TRIMETHYLSILYLCYCLOPENTANE ANNULATION CATIONIC POLYMERIZATION CONVENIENT ROUTE ALLYLTRIMETHYLSILANE <3+2>-CYCLOADDITION ALLYLSILYLATION REARRANGEMENT CONSTRUCTION ALKYNES ETHERS Aluminum chloride catalyzed stereoselective [3+2] cycloaddition of allylsilanes with simple conjugated dienes Article 10.1021/om970603s 1 ORGANOMETALLICS, v.16, no.24, pp.5158 - 5162 ORGANOMETALLICS 16 24 5158 5162 scie scopus A1997YJ37600009 2-s2.0-0000446955 Chemistry, Inorganic & Nuclear Chemistry, Organic Chemistry Article TRIMETHYLSILYLCYCLOPENTANE ANNULATION CATIONIC POLYMERIZATION CONVENIENT ROUTE ALLYLTRIMETHYLSILANE <3+2>-CYCLOADDITION ALLYLSILYLATION REARRANGEMENT CONSTRUCTION ALKYNES ETHERS [3+2] cycloaddition