Synonyms:K-selectride;L-selectride;N-selectride;selectride
99% *data from raw suppliers
L-SelectrideSolution(1.0?MinTHF) *data from reagent suppliers
F, 
C
The research investigates the Cope rearrangement and the selective reduction of acyclic ketones via electron-transfer-initiated processes. In the study of the Cope rearrangement, the chair and boat transition states were analyzed using CASSCF calculations. The chair transition state was found to have an energy of 40.7 kcal/mol above the CAS-optimized C2 geometry for 1,5-hexadiene, with an enthalpy of activation of 37.7 kcal/mol after correction for vibrational energy differences. The boat transition state had a higher energy and a larger value of R (2.316 ?) compared to the chair. The study found that both transition states are concerted and synchronous, contrasting with previous findings from AM1 and ab initio calculations. In the study of the selective reduction of acyclic ketones, various reducing agents were used, including LiAlH4, L-Selectride, Li-NH3, Li-NH3-NH4+, Na-EtOH, and SmI2. The results showed that reductions via electron-transfer-initiated processes, such as Birch reduction, Bouvault-Blanc reduction, and samarium iodide reduction, predominantly produced the anti-Cram isomer, while LiAlH4 and L-Selectride reductions produced the Cram isomer. The preference for the anti-Cram isomer in electron-transfer-initiated reductions is attributed to the relative stability of carbanion intermediates and the protonation step.
The research presents a simplified synthesis of (±)-4-hydroxy-N-methylmorphinan-6-one (2) and its methyl ether (3), which exhibit morphine-like antinociceptive activity. The synthesis involves several key steps and chemicals. Initially, the ketone 5 is reduced with L-Selectride in DMF and THF to obtain the triol 6. Subsequently, 6 is O-alkylated with 5-chloro-1-phenyl-1H-tetrazole in the presence of potassium carbonate to yield ethers 7 and 8. Hydrogenolysis of 7 over Pd/C in acetic acid produces acetate 10 and diol 9. Hydrolysis of 9 and 10 with methanolic HCl affords amine 11, which is then reductively N-methylated to form diol 12. Oppenauer oxidation of 12 with benzophenone and potassium tert-butoxide yields ketone 2 and an interesting byproduct, diphenylmethylene ketone 13. Additionally, O-methylation of 12 with phenyltrimethylammonium chloride produces ether alcohol 14, which upon further reaction yields the desired methyl ether 3. Finally, demethylation of 3 with BBr3 in chloroform gives phenol 2. The synthesized compounds 2 and 3 show significant antinociceptive activity, making them valuable for further pharmacological studies.
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