Robust, scalable, and highly selective spirocyclic catalysts for industrial hydroformylation and isomerization-hydroformylation.

Zong, Yan; Zhang, Runtong; Ma, Baode; Peng, Jianghua; Wu, Chao; Zou, Xiaomei; Qian, Yu; Chen, Gen-Qiang et al. · Sci Adv · 2024

basic_science · Level V

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Abstract

Hydroformylation (HF) or isomerization-hydroformylation (ISO-HF) represents the most direct and practical route for producing aldehydes on an industrial scale. To resolve the issues of low activity, low linear/branched (<i>l/b</i>) ratio, and low stability in HF and ISO-HF, we herein reported a class of spirocyclic diphosphites. Notably, the ligand termed <i>O</i>-SDPhite afforded excellent catalytic activity and regioselectivity for the HF of various olefins. Excellent <i>l/b</i> ratio and an unprecedented turnover number of up to 17,620,000 were achieved. <i>O</i>-SDPhite was also found to be effective in the regioselective ISO-HF of the industrially related cheap and abundant C4 <i>Raffinates</i> to <i>n</i>-valeraldehyde produced on a multimillion-ton scale. The reaction with <i>O</i>-SDPhite, superior to that of benchmark Biphephos, was continuously operated for 41 days and afforded an average 38.6 <i>l/b</i> ratio (31 days and 14.7 <i>l/b</i> ratio for Biphephos).