铜催化芳香醛和酮的氢硼化转化合成苄基硼酸酯类化合物

引用本文: 王露, 孙威, 刘超. 铜催化芳香醛和酮的氢硼化转化合成苄基硼酸酯类化合物[J]. 催化学报, 2018, 39(11): 1725-1729. doi: 10.1016/S1872-2067(18)63139-0 shu

Citation: Lu Wang, Wei Sun, Chao Liu. Cu-catalyzed deoxygenative gem-hydroborylation of aromatic aldehydes and ketones to access benzylboronic esters[J]. Chinese Journal of Catalysis, 2018, 39(11): 1725-1729. doi: 10.1016/S1872-2067(18)63139-0 shu

铜催化芳香醛和酮的氢硼化转化合成苄基硼酸酯类化合物

王露 ^a, ,
孙威 ^a,b, ,
刘超 ^a,

a 中国科学院兰州化学物理研究所苏州研究院, 羰基合成与选择氧化国家重点实验室, 甘肃兰州 730000;
b 中国科学院大学, 北京 100049
基金项目:
国家自然科学基金（91745110，21673261，21603245，21633013，21703265）；中科院兰州化物所“特聘人才”计划；中科院青年促进会（2018458）；中国化学会青年人才托举工程项目；中科院“西部之光”人才项目.

摘要: 有机硼化合物广泛应用于合成化学、药物化学以及材料化学等领域，开发新颖实用的方法合成有机硼化合物是重要的研究领域.在各种有机硼化合物中，苄基硼酸酯有着一些特有的性质，例如活性相对较高，可以有效地当作苄基化试剂使用.目前已有多种合成苄基硼酸酯的方法，主要集中在苄基格氏试剂或者锂试剂的硼化反应，但是该方法底物兼容性较差，而且苄基格氏试剂或者锂试剂的制备比较困难.随着催化反应的发展，过渡金属（如Pd，Cu，Ni，Fe）催化苄基卤代物的硼化反应及芳基卤代物和1，1-二硼类化合物的偶联反应能够有效地合成这类化合物.一级苄醇在钯或铜的催化作用下也可以转化为苄基硼酸酯.苄基C-H键的催化硼化是潜在的构建苄基硼酸酯的高原子经济性的方法，但目前其选择性和反应活性仍不高.在无金属催化的条件下，对甲苯磺酰腙类化合物与HBpin或B₂pin₂发生1，2-金属迁移是合成苄基硼酸酯的有效方法.到目前为止，虽然有很多种合成苄基硼酸酯的方法，但仍无法满足其合成需求，因此开发新型的方法合成苄基硼酸酯具有重要的意义.
本文开发了一种新型的铜催化芳香醛/酮类化合物的脱氧氢硼化转化体系.使用廉价易得的铜作为催化剂，叔丁醇钠或者叔丁醇钾作为碱，醇质子作为氢源，在100℃的条件下，芳香醛和芳香酮可直接转化成一级和二级苄基硼酸酯类化合物，该反应操作简单，反应体系可以兼容多种官能团，分离产率在21%-77%之间.反应机理方面，该转化有两种可能的过程，（1）反应体系中首先生成1，1-偕二硼化合物，该化合物在碱和EtOH的作用下发生脱硼质子解，最终转化成苄基单硼化合物；（2）醇质子转化成负氢物种，并与体系中的a-OBpin硼酸酯生成四配位硼，发生1，2-迁移后得到目标产物.
为了验证上述两种反应途径的可行性，我们进行了一系列的控制试验.首先合成了苯乙酮的1，1-二硼化合物，在催化量碱与当量醇的作用下，以99%的收率得到了脱硼质子解的产物，说明1，1-二硼化合物可以在反应体系中转化成苄基单硼化合物.以苯甲醛作为原料合成了a-OBpin硼酸酯，首先将其投入到甲醇、叔丁醇钠和B₂pin₂的体系中，最终得到了47%的苄基单硼；同时将a-OBpin硼酸酯投入到HBpin与叔丁醇钠的体系中，得到了57%的苄基单硼化合物，说明第二种反应过程通过1，2-迁移得到目标产物也是可行的.在当前的实验条件下，两种反应路径都是可能的.

关键词:

English

Cu-catalyzed deoxygenative gem-hydroborylation of aromatic aldehydes and ketones to access benzylboronic esters

a State Key Laboratory for Oxo Synthesis and Selective Oxidation, Suzhou Research Institute of Lanzhou Institute of Chemical Physics(LICP), LICP, Chinese Academy of Sciences, Lanzhou 730000, Gansu, China;
b University of Chinese Academy of Sciences, Beijing 100049, China
Received Date: 13 June 2018
Revised Date: 15 July 2018
Fund Project:
This work was supported by the National Natural Science Foundation of China (91745110, 21673261, 21603245, 21633013, 21703265) and a Start-up funding from LICP. Support from the Young Elite Scientist Sponsorship Program by CAST, CAS Interdisciplinary Innovation Team, the Key Program of CAS (QYZDJ-SSW-SLH051), the Youth Innovation Promotion Association CAS (2018458) and the ‘Light of West China’ Program.

Abstract: Organoboron compounds are widely used in synthetic chemistry, pharmaceutical chemistry and material chemistry. Among various organoboron compounds, benzylboronic esters are unique and highly reactive, making them suitable benzylation reagents. At present, the synthetic methods for the syntheses of benzylboronic esters are still insufficient to meet their demands. It is necessary to develop novel and practical methods for their preparation. In this work, a novel copper-catalyzed deoxygenative gem-hydroborylation of aromatic aldehydes and ketones has been developed. This direct and operationally simple protocol provides an effective approach for the synthesis of a variety of primary and secondary benzylboronates, in which broad functional group tolerance was presented. Widely available B₂pin₂ (pin=pinacol) was used as the boron source and alcoholic proton was applied as the hydride source.

Key words:

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铜催化芳香醛和酮的氢硼化转化合成苄基硼酸酯类化合物

English

Cu-catalyzed deoxygenative gem-hydroborylation of aromatic aldehydes and ketones to access benzylboronic esters

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

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CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

铜催化芳香醛和酮的氢硼化转化合成苄基硼酸酯类化合物

English

Cu-catalyzed deoxygenative gem-hydroborylation of aromatic aldehydes and ketones to access benzylboronic esters

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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