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

• 成果类型: Article
• 署名作者: Sun, Qiu; Belting, Jan-Niklas; Hauda, Julian; Tymann, David; Antoni, Patrick W.; Goddard, Richard; Hansmann, Max M.
• 署名单位: Dortmund University of Technology; Max Planck Society
• 刊物名称: SCIENCE
• ISSN/ISSBN: 0036-12175
• DOI: 10.1126/science.ads5974
• 发表日期: 2025-02-21
• 页码: 885-892
• 关键词: atomic carbon; DECOMPOSITION; chemistry; diazocyclopropane; transformations; equivalents

摘要

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(sp(3))-atom surrounded by four sigma-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=N-2 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(sp(3))-atom. New C-C and C-X (where X is O or N) bonds can be created around the C(sp(3))-atom, which can ultimately be extended to four C-C sigma-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.