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Rh-catalyzed selective synthesis of 1,5-dimethylhexahydro-1H-inden-4(2H)-one via hydroformylation of (R)-carvone
Catalysis Communications ( IF 3.7 ) Pub Date : 2018-04-21
Sachin S. Bhagade, Bhalchandra M. Bhanage

This work reports domino hydroformylation, hydrogenation and intramolecular keto-aldol condensation reactions for the selective synthesis of 1,5-dimethylhexahydro-1H-inden-4(2H)-one obtained from (R)-carvone and dihydrocarvone under homogeneous hydroformylation condition. The synthesis of the desired product was achieved by using conventional rhodium/1,3-bis(diphenylphosphino)propane (Rh/dppp) catalyst and PPTS (pyridinium p-toluenesulfonate) as an acidic co-catalyst. The reaction conditions were optimized with respect to various reaction parameters like time, temperature, synthesis gas (CO/H2) pressure, solvents, catalyst and co-catalyst loading. The experimental results showed that less planner carbon backbone in dihydrocarvone increases the steric hindrance around the reaction site and responsible for the reactivity difference between (R)-carvone and dihydrocarvone.



中文翻译:

铑催化的1,5-二甲基六-1H-茚-4(2H) -酮的选择性合成通过的加氢甲酰化([R )-香芹酮

这项工作报告多米诺加氢甲酰化,加氢和分子内的酮-醛醇缩合反应,用于在均相加氢甲酰化条件下选择性合成由(R)-香芹酮和二氢香芹酮制得的1,5-二甲基六氢-1H-inden-4(2H)- 。通过使用常规的铑/ 1,3-双(二苯基膦基)丙烷(Rh / dppp)催化剂和PPTS(甲苯磺酸吡啶鎓)作为酸性助催化剂,可以实现所需产物的合成。针对各种反应参数(例如时间,温度,合成气(CO / H 2))对反应条件进行了优化)压力,溶剂,催化剂和助催化剂的负载量。实验结果表明,二氢香芹酮中较少的规划碳主链增加了反应位点附近的空间位阻,并造成了(R)-香芹酮与二氢香芹酮之间的反应性差异。

更新日期:2018-04-25
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