Chemoselective Hydrogenolysis of Urethanes to Formamides and Alcohols in the Presence of More Electrophilic Carbonyl Compounds

被引：4

作者：

Iwasaki, Takanori ^{[1
]}

Yamada, Yuto ^{[1
]}

Naito, Naoki ^{[1
,2
]}

Nozaki, Kyoko ^{[1
]}

机构：

[1] Univ Tokyo, Grad Sch Engn, Dept Chem & Biotechnol, Tokyo 1138656, Japan

[2] Harvard Univ, Dept Chem & Chem Biol, Cambridge, MA 02138 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2024年 / 146卷 / 37期

关键词：

CATALYTIC-HYDROGENATION; FOAM WASTE; DERIVATIVES; DECOMPOSITION; POLYURETHANES; CONVERSION;

D O I：

10.1021/jacs.4c06553

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The development of methods for the chemical recycling of polyurethanes is recognized as an urgent issue. Herein, we report the Ir-catalyzed hydrogenolysis of the urethane C-O bond to produce formamides and alcohols, where both formamides and ester and amide functionalities are tolerated. The chemoselectivity observed is counterintuitive to the generally accepted electrophilicity order of carbonyl compounds. Hydrogenolysis of urea and isocyanurate, potential byproducts in the polycondensation process of polyurethanes, is also achieved alongside the selective degradation of polyurethanes themselves, which affords diformamides and diols. The time-course of the hydrogenative polyurethane degradation reveals that the bond cleavage occurs not from the terminal, but from any part of the polymer chain. The present catalysis offers a novel method for the recycling of polyurethane-containing polymer waste.

引用

页码：25562 / 25568

页数：7

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