期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 136, 期 38, 页码 13453-13457出版社
AMER CHEMICAL SOC
DOI: 10.1021/ja5077525
关键词
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资金
- NSERC of Canada
- Canada Research Chair
- NSERC-CGS-D
- Bristol Chemical Synthesis Doctoral Training Centre
- SKLEST of China [ZDKT1203]
Aromatic hydrogenation is a challenging transformation typically requiring alkali or transition metal reagents and/or harsh conditions to facilitate the process. In sharp contrast, the aromatic heterocycle 2,4,6-tri-tert-butyl-1,3,5-triphosphabenzene is shown to be reduced under 4 atm of H-2 to give [3.1.0]bicylo reduction products, with the structure of the major isomer being confirmed by X-ray crystallography. NMR studies show this reaction proceeds via a reversible 1,4-H-2 addition to generate an intermediate species, which undergoes an irreversible suprafacial hydride shift concurrent with P P bond formation to give the isolated products. Further, para-hydrogen experiments confirmed the addition of H-2 to triphosphabenzene is a bimolecular process. Density functional theory (DFT) calculations show that facile distortion of the planar triphosphabenzene toward a boat-conformation provides a suprafacial combination of vacant acceptor and donor orbitals that permits this direct and uncatalyzed reduction of the aromatic molecule.
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