Origin of site-selectivity of hydrogen atom transfer in carbohydrate C-H alkylations via photoredox catalysis

被引：3

作者：

Ji, Yujie ^{[1
]}

Hu, Lingfei ^{[1
]}

Gao, Han ^{[1
]}

Wu, Yan-Bo ^{[2
,3
]}

Lv, Xiangying ^{[1
]}

Lu, Gang ^{[1
]}

机构：

[1] Shandong Univ, Sch Chem & Chem Engn, Key Lab Colloid & Interface Chem, Minist Educ, Jinan 250100, Shandong, Peoples R China

[2] Shanxi Univ, Key Lab Mat Energy Convers & Storage Shanxi Prov, Taiyuan 030006, Shanxi, Peoples R China

[3] Shanxi Univ, Inst Mol Sci, Key Lab Chem Biol & Mol Engn, Minist Educ, Taiyuan 030006, Shanxi, Peoples R China

来源：

ORGANIC CHEMISTRY FRONTIERS | 2024年 / 11卷 / 08期

基金：

中国国家自然科学基金;

关键词：

RADICALS; FUNCTIONALIZATION; ACTIVATION; OXIDATION; STRATEGY; SUGARS; BONDS; HAT;

D O I：

10.1039/d4qo00073k

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The mechanism and origin of site-selectivity in carbohydrate C-H alkylations via photoredox catalysis were investigated using DFT calculations and the approach of energy decomposition analysis. The results reveal that diphenylborinic acid can promote the reactivity by lowering the barrier of the lactonization process. The effect of diphenylborinic acid on the site-selectivity of HAT is mostly due to the enhanced charge transfer from the sugar C-H sigma orbital to the nitrogen SOMO of the quinuclidine radical cation. An effective binary linear regression model, including C-H sigma orbital energy and C-H BDE, has been proposed for predicting the site-selectivity of the sugar HAT process.

引用

页码：2269 / 2276

页数：8

共 73 条

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