Spiro-C(sp³)-atom transfer: Creating rigid three-dimensional structures with Ph₂SCN₂.

IF 44.7 1区综合性期刊 Q1 MULTIDISCIPLINARY SCIENCES Science Pub Date : 2025-02-21 Epub Date: 2025-02-20 DOI:10.1126/science.ads5974

Qiu Sun, Jan-Niklas Belting, Julian Hauda, David Tymann, Patrick W Antoni, Richard Goddard, Max M Hansmann

引用次数: 0

Abstract

The introduction of a single C-atom into organic substrates typically results in the formation of flat molecules containing unsaturated C(sp)-centers. Adding a single C(sp³)-atom surrounded by four σ-C-C bonds, which opens up the three-dimensional space, is an unresolved problem in synthetic chemistry. We report the synthesis and application of the diazosulfur ylide Ph₂S=C=N₂ reagent that combines the reactivity of both sulfur ylides and diazo compounds to create carbon spiro-centers in a general fashion by the sequential or single-step installation of a C(sp³)-atom. New C-C and C-X (where X is O or N) bonds can be created around the C(sp³)-atom, which can ultimately be extended to four C-C σ-bonds in one step without resorting to transition metal catalysis. Ph₂SCN₂ can also be used to access highly strained frameworks containing (oxa)spiro[2.2]pentanes as well as tricyclic spiro-compounds.

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在有机基质中引入单个 C 原子通常会形成含有不饱和 C（sp）中心的扁平分子。添加由四个 σ-C-C 键包围的单个 C(sp3)原子，从而打开三维空间，是合成化学中一个尚未解决的问题。我们报告了重氮硫酰亚胺 Ph2S=C=N2 试剂的合成和应用，该试剂结合了硫酰亚胺和重氮化合物的反应活性，通过顺序或单步安装 C（sp3）原子，以通用方式创建碳螺中心。新的 C-C 键和 C-X（其中 X 为 O 或 N）键可围绕 C（sp3）原子生成，最终可在不使用过渡金属催化的情况下一步扩展为四个 C-C σ 键。Ph2SCN2 还可用于获得含有 (oxa)spiro[2.2]pentanes 和三环螺化合物的高应变框架。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Science 综合性期刊-综合性期刊

CiteScore

61.10

自引率

0.90%

发文量

审稿时长

2.1 months

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Spiro-C(sp3)-atom transfer: Creating rigid three-dimensional structures with Ph2SCN2.

Abstract

Spiro-C(sp³)-atom transfer: Creating rigid three-dimensional structures with Ph₂SCN₂.