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Catalytic Ring Expansion of Furyl Hydrosilanes: Synthesis of 1,2‐Oxasilines as Diels‐Alder Diene Components
Author(s) -
He Qiaoxing,
Xu Zheyuan,
Fang Huaquan,
Liu Sifan,
Lu Xi,
Hong Xin,
Fu Yao,
Liu Guixia,
Huang Zheng
Publication year - 2025
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202425232
Subject(s) - furan , regioselectivity , ring (chemistry) , reactivity (psychology) , chemistry , diene , ruthenium , hydride , catalysis , organic synthesis , combinatorial chemistry , organic chemistry , metal , natural rubber , medicine , alternative medicine , pathology
Abstract The development of new methods for aromatic ring‐expansion offers a strategic means of transforming abundant aromatic feedstocks into intricate structures via skeletal editing, thereby unlocking valuable avenues for organic synthesis. We report herein a mild and efficient ruthenium‐catalyzed ring‐expansion of 2‐silylfurans to form 1,2‐oxasilines with wide substrate scope and excellent functional group tolerance. Density functional theory (DFT) calculations suggest the reaction proceeds through regioselective insertion of furan double bond into a Ru─H bond, followed by skeletal rearrangement, 1,2‐hydride transfer, and elimination steps. The resulting 1,2‐oxasilines are electron‐rich cyclic dienes with an extrudable and transformable Si─O linker, which exhibit unique and versatile reactivity in Diels–Alder cyclization with electron‐deficient dienophiles, enabling modular assembly of molecular skeletons with higher complexity.