C2-ketonylation of carbohydrates via excited-state palladium-catalyzed 1,2-spin-center shift,Chemical Science

当前位置： X-MOL 学术 › Chem. Sci. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

C2-ketonylation of carbohydrates via excited-state palladium-catalyzed 1,2-spin-center shift
Chemical Science ( IF 7.6 ) Pub Date : 2022-05-11 , DOI: 10.1039/d2sc01042a
Gaoyuan Zhao ₁ , Upasana Mukherjee ₁ , Lin Zhou ₂ , Yue Wu ₂ , Wang Yao ₁ , Jaclyn N Mauro ₁ , Peng Liu ₂ , Ming-Yu Ngai ₁

Affiliation

C2-ketonyl-2-deoxysugars, sugars with the C2-hydroxyl group replaced by a ketone side chain, are important carbohydrate mimetics in glycobiology and drug discovery studies; however, their preparation remains a vital challenge in organic synthesis. Here we report the first direct strategy to synthesize this class of glycomimetics from readily available 1-bromosugars and silyl enol ethers via an excited-state palladium-catalyzed 1,2-spin-center shift (SCS) process. This step-economic reaction features broad substrate scope, has a high functional group tolerance, and can be used in late-stage functionalization of natural product- and drug-glycoconjugates. Preliminary experimental and computational mechanistic studies suggested a non-chain radical mechanism involving photoexcited palladium species, a 1,2-SCS process, and a radical Mizoroki–Heck reaction.

中文翻译：

通过激发态钯催化的 1,2-自旋中心转移进行碳水化合物的 C2 酮基化

C2-酮基-2-脱氧糖是 C2-羟基被酮侧链取代的糖，是糖生物学和药物发现研究中重要的碳水化合物模拟物；然而，它们的制备仍然是有机合成中的一个重大挑战。在这里，我们报告了第一个直接策略，通过激发态钯催化的 1,2-自旋中心转移 (SCS) 过程，从容易获得的 1-溴糖和硅烯醇醚合成此类糖模拟物。该步骤经济的反应具有底物范围广、官能团耐受性高的特点，可用于天然产物和药物糖复合物的后期功能化。初步实验和计算机理研究表明，非链自由基机制涉及光激发钯物质、1,2-SCS 过程和自由基 Mizoroki-Heck 反应。

更新日期：2022-05-11

点击分享查看原文

点击收藏

公开下载

阅读更多本刊新发论文本刊介绍/投稿指南