Acylative Kinetic Resolution of Alcohols Using a Recyclable Polymer-Supported Isothiourea Catalyst in Batch and Flow
Acylative Kinetic Resolution of Alcohols Using a Recyclable Polymer-Supported Isothiourea Catalyst in Batch and Flow
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DOI：
10.1021/acscatal.7b04001
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发表时间：
2018-01
期刊：
影响因子：
12.9
通讯作者：
Rifahath M. Neyyappadath;R. Chisholm;M. Greenhalgh;Carles Rodríguez-Escrich;M. A. Pericàs;G. Hähner;Andrew D. Smith
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文献类型：
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作者：
Rifahath M. Neyyappadath;R. Chisholm;M. Greenhalgh;Carles Rodríguez-Escrich;M. A. Pericàs;G. Hähner;Andrew D. Smith
以均相催化剂HyperBTM为基础，制备了聚苯乙烯负载的异硫代巴比妥催化剂，并用于仲醇的酰化动力学拆分。广泛的醇，包括苄，烯丙基，和炔丙醇，环烷醇衍生物，和1，2-二醇，已解决使用丙酸或异丁酸酐具有良好的到优秀的选择性因子获得（28例，s值高达600）。催化剂可以通过简单的过滤和洗涤程序回收和重复使用，无需特殊的预防措施。证明了催化剂的可再循环性（15次循环），活性或选择性均无显著损失。该可循环催化剂还用于使用不同酸酐连续拆分10种不同醇，循环之间无交叉污染。最后，在连续流动过程中的成功应用证明了固定化刘易斯碱催化剂用于动力学拆分的第一例。
A polystyrene-supported isothiourea catalyst, based on the homogeneous catalyst HyperBTM, has been prepared and used for the acylative kinetic resolution of secondary alcohols. A wide range of alcohols, including benzylic, allylic, and propargylic alcohols, cycloalkanol derivatives, and a 1,2-diol, has been resolved using either propionic or isobutyric anhydride with good to excellent selectivity factors obtained (28 examples, s values up to 600). The catalyst can be recovered and reused by a simple filtration and washing sequence, with no special precautions needed. The recyclability of the catalyst was demonstrated (15 cycles) with no significant loss in either activity or selectivity. The recyclable catalyst was also used for the sequential resolution of 10 different alcohols using different anhydrides with no cross-contamination between cycles. Finally, successful application in a continuous flow process demonstrated the first example of an immobilized Lewis base catalyst used for the kinetic resoluti...