Evaluating polymer-supported isothiourea catalysis in industrially-preferable solvents for the acylative kinetic resolution of secondary and tertiary heterocyclic alcohols in batch and flow,Green Chemistry

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Evaluating polymer-supported isothiourea catalysis in industrially-preferable solvents for the acylative kinetic resolution of secondary and tertiary heterocyclic alcohols in batch and flow
Green Chemistry ( IF 9.3 ) Pub Date : 2018-08-24 , DOI: 10.1039/c8gc02020e
Nitul Ranjan Guha _{1,

2,

3,

4,

5} , Rifahath M. Neyyappadath _{1,

2,

3,

4,

5} , Mark D. Greenhalgh _{1,

2,

3,

4,

5} , Ross Chisholm _{1,

2,

3,

4,

5} , Samuel M. Smith _{1,

2,

3,

4,

5} , Megan L. McEvoy _{1,

2,

3,

4,

5} , Claire M. Young _{1,

2,

3,

4,

5} , Carles Rodríguez-Escrich _{6,

7,

8,

9} , Miquel A. Pericàs _{6,

7,

8,

9,

10} , Georg Hähner _{1,

2,

3,

4,

5} , Andrew D. Smith _{1,

2,

3,

4,

5}

Affiliation

Polymer-supported Lewis base catalysts, based on the homogeneous isothioureas HyperBTM and BTM, have been synthesised and applied for the acylative kinetic resolution of secondary and tertiary heterocyclic alcohols. In batch, the use of industrially-preferable solvents was investigated, with dimethyl carbonate proving to be most generally-applicable. Significantly, the HyperBTM-derived immobilised catalysts were readily recycled, with no loss in either activity or selectivity. In addition to the kinetic resolution of secondary benzylic, propargylic, allylic and cycloalkanol derivatives, a range of 22 tertiary heterocyclic alcohols, based on privileged 3-hydroxyoxindole and 3-hydroxypyrrolidinone substructures, were resolved with up to excellent selectivity (s = 7–190). Finally, the immobilised isothiourea catalysts were applied in a packed bed reactor to demonstrate the first example of the kinetic resolution of tertiary heterocyclic alcohols in a continuous flow process. High selectivities were obtained for the resolution of 3-hydroxyoxindole derivatives in ethyl acetate (s up to 70); and for 3-hydroxypyrrolidinones derivatives in toluene (s up to 42).

中文翻译：

在工业首选溶剂中评估聚合物负载的异硫脲催化批次和流动中仲和叔杂环醇的酰基动力学拆分

已经合成了基于均相异硫脲HyperBTM和BTM的聚合物负载的路易斯碱催化剂，并将其用于仲和叔杂环醇的酰基动力学拆分。分批地，研究了工业上优选的溶剂的使用，其中碳酸二甲酯被证明是最普遍适用的。重要的是，HyperBTM衍生的固定化催化剂易于回收利用，而活性或选择性均没有损失。除了动力学拆分二级苄基，炔丙基，烯丙基和环烷醇衍生物外，还基于优选的3-羟基羟吲哚和3-羟基吡咯烷酮亚结构对22种叔杂环醇进行了分离，分离度高达出色的（s= 7–190）。最后，将固定化的异硫脲催化剂应用于填充床反应器中，以证明连续流动过程中叔杂环醇动力学拆分的第一个实例。3-hydroxyoxindole衍生物在乙酸乙酯（分辨率获得高选择性š高达70）; 和3- hydroxypyrrolidinones衍生物在甲苯（š高达42）。

更新日期：2018-10-01

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