145198-93-2

Upstream product

• 1201224-26-1 2-methylpent-4-enyl (N-p-toluenesulfonyl)carbamate 
• 60523-21-9 ethyl 2-methyl-3,4-pentadienoate 
• 155354-81-7 2-methyl-3,4-pentadienyl tosylcarbamate 
• 4083-64-1 Tosyl isocyanate 
• 145198-81-8 5-Methyl-4-vinyl-[1,3]dioxan-2-one 
• 26674-94-2 2-methylpenta-3,4-dien-1-ol 

Downstream Products

• 145198-97-6 trans-N-(p-Toluenesulfonyl)-3-methyl-2-vinylazetidine 
• 145198-97-6 cis-N-(p-Toluenesulfonyl)-3-methyl-2-vinylazetidine 

Relevant academic research and scientific papers

Striking AcOH acceleration in direct intramolecular allylie amination reactions

An experiment was conducted to demonstrate that a strong accelerating effect occurs in direct intramolecular allylic amination when the reaction is conducted in AcOH rather than in CHCl or THF. A round bottom flask under air was charged with N-tosylcarbamate 3a-j, Pd(OAc)2, bis-sulfoxide ligand LL, phenylbenzoquinone and AcOH. The reaction was allowed to stir at 45°C for 24 h. The reaction mixture was hydrolysed and extracted with AcOEt. The combined organic layers were dried over MgSO4, filtered, and concentrated in vacuo. Cyclisation of 3a was repeated in CH2Cl 2 and in AcOH by using stoichiometric amounts of Pd(OAc) without benzoquinone. Stoichiometric tests and computational DFT analysis of the palladium reoxidation step provide an overview of the structural and energetic role of acetic acid in increasing the efficacy of the entire catalytic cycle.

Silver(I)-catalyzed aminocyclization of 2,3-butadienyl and 3,4-pentadienyl carbamates: An efficient and stereoselective synthesis of 4-vinyl-2-oxazolidinones and 4-vinyltetrahydro-2H-1,3-oxazin-2-ones

Silver(I) salts in combination with an appropriate base (mostly triethylamine) catalyzed the aminocyclization of N-substituted 2,3-butadienyl carbamates 1 (benzene, 50°C) to provide 4-vinyl-2-oxazolidinones 2 in good yields. The stereoselectivity (trans-2/cis-2) ranged from 1.4 for C5-Me to >30 for C5-phenyl, isopropenyl, and t-butyl derivatives. 3,4-Pentadienyl tosylcarbamates 3, the one-carbon higher homologues of 1, underwent a similar cyclization to give 4-vinyltetrahydro-2H-1,3-oxazin-2-one 4 in synthetically useful yields and in higher trans selectivities than 1.

Regio- and stereoselective synthesis of 1,3-hydroxyl amines via palladium-catalyzed carbonate-carbamate transformation with unique stereoselectivity: Synthesis of 3-amino-4-penten-1-ols

The transformation of cyclic carbonates 1 to cyclic carbamates 4 is achieved in the presence of aryl or sulfonyl isocyanate by the catalysis of Pd(0) in high yield and with high structural flexibility. The reaction shows unique stereoselectivity: 3,4-disubstituted carbonates 2, irrespective of the composition of their stereoisomers, provide trans-5 exclusively or predominantly over cis-5. Mixtures of cis- and trans-3,5-disubstituted carbonates 3 furnish either cis-6 or trans-6 in high selectivity depending on the reaction conditions (kinetic or thermodynamic control, respectively). 1H NMR and X-ray structure analyses of 5 and 6 indicate that the stereochemical outcome is governed by an A1,2-strain between N-sulfonyl and C5-vinyl substituents.

Palladium-catalysed Regio- and Stereo-selective Synthesis of Allylic Amines

3-Vinyl-2,6-dioxacyclohexan-1-ones 1, by treatment with N-tosyl or N-arylisocyanates and a catalytic amount of Pd0, are converted into N-tosyl- and N-aryl-3-vinyl-2-aza-6-oxacyclohexan-1-ones 2 in good yields and with unique stereoselectivity.