Carbene-Catalyzed Enantioselective Addition of Sulfinate to Ketones,Organic Letters

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Carbene-Catalyzed Enantioselective Addition of Sulfinate to Ketones
Organic Letters ( IF 4.9 ) Pub Date : 2024-05-14 , DOI: 10.1021/acs.orglett.4c01473
Rui Deng ₁ , Mingyi Pan ₁ , Jianjian Liu ₁ , Pengcheng Zheng ₁ , Yonggui Robin Chi _{1,

2}

Affiliation

A carbene-catalyzed enantioselective addition of sulfinate to ketones between 2-benzoylbenzaldehyde and sulfonyl chloride is disclosed. Up to now, the carbon and heteroatom nucleophiles have effectively undergone catalytic enantioselective addition to carbonyl molecules to introduce functionalities and chirality. Sulfone, as an important class of sulfur-containing functional groups, represents highly valuable motifs in medicines and natural products. It remains undeveloped for the catalytic asymmetric addition of sulfinate to carbonyls. Herein we disclosed the first catalytic enantioselective addition of sulfinate to ketones for the synthesis of sulfones via N-heterocyclic carbene (NHC) catalysis. The sulfonyl chloride behaves both as an oxidant and as a nucleophilic substrate in this carbene-catalyzed process. Experimental studies suggested that the Breslow intermediate can be SET oxidized by sulfonyl chloride to generate the sulfonyl radical. This novel synthetic approach for the asymmetric addition of sulfinate to carbonyls can also be used to modify the commercially available functional molecules.

中文翻译：

卡宾催化亚磺酸盐与酮的对映选择性加成

公开了在2-苯甲酰基苯甲醛和磺酰氯之间卡宾催化的亚磺酸盐与酮的对映选择性加成。到目前为止，碳和杂原子亲核试剂已有效地与羰基分子进行催化对映选择性加成，以引入官能团和手性。砜作为一类重要的含硫官能团，在药物和天然产物中代表着非常有价值的基序。亚磺酸盐与羰基的催化不对称加成尚未开发出来。在此，我们首次公开了亚磺酸盐与酮的催化对映选择性加成，通过 N-杂环卡宾 (NHC) 催化合成砜。在卡宾催化过程中，磺酰氯既充当氧化剂又充当亲核底物。实验研究表明Breslow中间体可以被磺酰氯SET氧化生成磺酰自由基。这种将亚磺酸盐不对称加成到羰基上的新颖合成方法也可用于修饰市售的功能分子。

更新日期：2024-05-14

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