200437-33-8

Upstream product

• 6909-30-4 (1S,2R,4R)-limonene-1,2-epoxide 
• 1195-92-2 (4R)-limonene 1,2-epoxide 
• 5989-27-5 D-limonene 

Downstream Products

• 66511-82-8 (1S,2S,4R)-2-amino-1-methyl-4-(1-methylethenyl)cyclohexanol 

Relevant academic research and scientific papers

Chiral amino and imino-alcohols based on (R)-limonene

Derivatives of the natural occurring and inexpensive terpene (R)-limonene were synthetized and completely characterized. Starting from internal olefin epoxidation, followed by epoxide opening with sodium azide and azide reduction with LiAlH4, two chiral amino-alcohols were obtained. The amino-alcohols were reacted with three different aldehydes, generating six new imino-alcohols, two of them yielding crystals suitable for X-ray diffraction characterization. The reduction of four of these compounds with LiAlH4 led to new amino-alcohols. All derivatives were obtained with good overall yields through simple reaction protocols.

Synthesis and reactions of highly strained 2,3-bridged 2H-azirines

Take the strain: Despite extreme ring strain and reactivity, the heterocycles 2, which are easily obtained from azides 1 and detectable by NMR spectroscopy, can be converted stereoselectively by novel addition and cycloaddition reactions. (Chemical Equation Presented)

Regio- and stereoselectivity of diethylaluminum azide opening of trisubstituted epoxides and conversion of the 3° azidohydrin adducts to isoprenoid aziridines

The regioisomer ratios (3°,2°/2°,3°), and in some cases the stereochemistry, of vicinal azidohydrins formed in reactions of 11 trisubstituted terpene epoxides with Et2AlN3 in toluene are reported. The more highly substituted azide usually predominated (3°,2°/2°,3° ratios ≥ 40:1 to 2.5-1) in accord with a Markovnikov orientation and an SN1-like transition state. Reversed regioisomer ratios were observed with 6,7-epoxygeranyl acetate (1:2.5) and cis-1,2-epoxylimonene (1:3.3 to 1:10). The tertiary azido diols from 2,3-epoxygeraniol, 2,3-epoxyfarnesol, and 2,3-epoxynerol were formed as single isomers with inversion of configuration at C3 (≥ 35-40:1 for the C10 azido diols). The regioselectivity was affected by the presence and proximity of oxy functional groups on the epoxide substrate (OH, OAc, and OSi-tBuMe2), the equivalents of Et2AlN3, and additives (EtOAc or EtOH). The results and trends are rationalized by consideration of the structural and stereoelectronic characteristics of proposed diethylaluminum epoxonium ion intermediates and transition states, together with the nucleophilicity of the azide donor. Six of the 3°,2° azidohydrins were converted to the corresponding aziridines by primary-selective silylations of four azido diols, mesylations, and reductive cyclizations with LiAlH4.

Ring opening reaction of epoxides with diphenyl phosphorazidate

Diphenyl phosphorazidate with 4-dimethylaminopyridine and lithium perchlorate opens epoxides regio- and stereoselectively to give O- diphenylphosphoryl vicinal azidohydrins: For the α,β-epoxy ketones and esters, only the corresponding α-azidovinyl ketones