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Synthesis, Structure, and Properties of Twofold Bridged Sesquinorbornenes
Author(s) -
Griesbeck Axel G.,
Deufel Thomas,
Hohlneicher Georg,
Rebentisch Rupert,
Steinwascher Jörg
Publication year - 1998
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/(sici)1099-0690(199809)1998:9<1759::aid-ejoc1759>3.0.co;2-i
Subject(s) - chemistry , dimethyldioxirane , benzoquinone , reactivity (psychology) , ab initio , singlet state , dioxirane , singlet oxygen , computational chemistry , ab initio quantum chemistry methods , crystal structure , stereochemistry , crystallography , oxygen , molecule , photochemistry , organic chemistry , excited state , medicine , physics , alternative medicine , pathology , nuclear physics
The twofold bridged sesquinorbornenes 2 and 6 were prepared using sequential [4 + 2] cycloadditions of benzoquinone with 1,5‐dihydropentalenes 1 and 5 . These syntheses were improved using dilution conditions or a more reactive substituted benzoquinone. Results from semiempirical and ab initio DFT calculations indicated remarkably high pyramidalization angles (ϕ = 46‐47°) for the central C–C double‐bond atoms. The chemical reactivity with triplet and singlet oxygen, dimethyldioxirane and N ‐methyl‐1,2,4‐triazoline‐3,5‐dione supports these structural assignments.