Regioselective Hydroxymethylation of Alkenes to Linear Alcohols with CO2/H2 Using a Rh/Ru Dual Catalyst
Regioselective Hydroxymethylation of Alkenes to Linear Alcohols with CO2/H2 Using a Rh/Ru Dual Catalyst
复制标题
使用 Rh/Ru 双催化剂通过 CO2/H2 将烯烃区域选择性羟甲基化为直链醇
DOI：
10.1021/acssuschemeng.1c06057
复制
发表时间：
2021-12
影响因子：
8.4
通讯作者：
Sun Yuhan
中科院分区：
文献类型：
--
作者：
Hua Kaimin;Liu Xiaofang;Chen Junjun;Wei Baiyin;Wang Hui;Sun Yuhan
co2是一种有吸引力的可再生C1资源，h2是一种廉价的绿色还原剂。二氧化碳和氢的结合为烯烃的羟甲基化提供了一种新的合成工具，可以直接生成醇类，特别是线性醇类，它们通常是洗涤剂和增塑剂的前体。然而，这种有前途的转化的最大问题是由于无法对配体进行区域选择性控制而导致的非区域选择，这是由于反向水气转换步骤所需的高温造成的。在这里，我们开发了一种创新的策略，通过配体的区域可控能力，选择性地从烯烃和CO2/ h2生产线性醇。以PTA（1,3,5-三氮杂-7-磷adamantane）为配体的双金属铑钌催化剂有效地催化了该反应，得到的醇的收率高达92%，区域选择性为87/13，超过了已有的报道。机理研究表明，转化过程是通过多米诺骨牌序列进行的，即co2加氢成HCOOH、CO快速释放、氢甲酰化和醛还原。Rh和Ru的协同作用促进了多米诺骨牌序列的完美实现，而配体PTA则很好地调节了区域选择性。值得注意的是，Ru/PTA对co2和醛的优先加氢抑制了烯烃异构化和加氢的发生，这在其他配体中是不存在的。该策略通过配体的区域可控能力，为选择性生产线性醇和CO2转化开辟了一条新途径，这将为工业上的CO2羰基化提供启示。
CO2is an attractive renewable C1 resource, and H2is a cheap and green reductant. The combination of CO2and H2for hydroxymethylation of alkenes provides a novel synthetic tool to directly generate alcohols, especially linear ones, which are generally preferred as precursors of detergents and plasticizers. However, the most problematic issue of this promising transformation is the non-regioselection due to the inability of regioselectivity control over the ligand, resulting from the high temperature required for the reverse water–gas shift step. Here, we develop an innovative strategy to selectively produce linear alcohols from alkenes and CO2/H2through the regiocontrollable ability of the ligand. The reaction is efficiently mediated by a bimetallic Rh–Ru catalyst using PTA (1,3,5-triaza-7-phosphaadamantane) as the ligand, and the desired alcohols can be obtained in up to 92% yield with 87/13 regioselectivity, which surpasses that ever reported. The mechanistic study reveals that the transformation proceeds through domino sequences, that is, CO2hydrogenation to HCOOH, fast release of CO, hydroformylation, and aldehyde reduction. The synergy of Rh and Ru contributes to the excellent fulfillment of the domino sequences, while the ligand PTA regulates the regioselectivity elegantly. Notably, the preferred hydrogenation of CO2and aldehydes by Ru/PTA inhibits the occurrence of alkene isomerization and hydrogenation, which is not available in other ligands. The strategy opens a new way for selective production of linear alcohols together with CO2transformation through the regiocontrollable ability of the ligand, which will shed light on industrial carbonylation with CO2.
登录
查看更多内容
影响因子：
62.1
作者：
Álvarez A;Bansode A;Urakawa A;Bavykina AV;Wezendonk TA;Makkee M;Gascon J;Kapteijn F
通讯作者：
Kapteijn F
调节Na和Co2C之间的相互作用以促进CO2选择性加氢生成乙醇
DOI：
10.1016/j.apcatb.2021.120207
发表时间：
2021-04
期刊：
Applied Catalysis B: Environmental
影响因子：
--
作者：
Zhang Shunan;Wu Zhaoxuan;Liu Xiaofang;Shao Zilong;Xia Lin;Zhong Liangshu;Wang Hui;Sun Yuhan
通讯作者：
Sun Yuhan
高效、选择性和可持续的二氧化碳催化
影响因子：
9.8
作者：
Song Qing-Wen;Zhou Zhi-Hua;He Liang-Nian
通讯作者：
He Liang-Nian
过渡金属催化的不饱和底物与 CO2 的羧化反应
影响因子：
20.6
作者：
Yan Si-Shun;Fu Qiang;Liao Li-Li;Sun Guo-Quan;Ye Jian-Heng;Gong Li;Bo-Xue Yin-Zi;Yu Da-Gang
通讯作者：
Yu Da-Gang
影响因子：
2.8
作者：
Piotr Smoleński;A. Kirillov;M. Silva;A. Pombeiro
通讯作者：
Piotr Smoleński;A. Kirillov;M. Silva;A. Pombeiro