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η 6 ‐(1‐oxobenzocyclobutene)tricarbonylchromium(0): Preparation, reduction, and ring‐opening/cycloaddition chemistry of the 1‐hydroxybenzocyclobutene complex
Author(s) -
Brands Michael,
Wey Hans G.,
Krömer Rainer,
Krüger Carl,
Butenschön Holger
Publication year - 1995
Publication title -
liebigs annalen
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 0947-3440
DOI - 10.1002/jlac.199519950235
Subject(s) - chemistry , cycloaddition , methyl vinyl ketone , ring (chemistry) , enantiomer , chirality (physics) , stereochemistry , medicinal chemistry , organic chemistry , catalysis , chiral symmetry breaking , physics , quantum mechanics , nambu–jona lasinio model , quark
The syntheses of the tricarbonylchromium complexes 2 and 3 of 1‐oxobenzocyclobutene and 1‐hydroxybenzocyclobutene are described. Alcoholate 6 of 3 undergoes a ring opening to the corresponding ortho ‐quinodimethane intermediate between −30 and −20°C, which is trapped by dienophiles with high diastereoselectivity. While with most dienophiles products with a 1,2‐ cis configuration ( 7, 8, 10 ) are formed, vinyl sulfones react in an exo ‐selective cycloaddition with formation of 1,2‐ trans ‐configurated cycloadducts ( 12, 13 ). The configuration of the cycloadduct with phenyl vinyl sulfone is confirmed by an X‐ray crystal structure analysis. As one of the important aspects of the chemistry of benzocyclobutene complexes is the chirality of compounds like 2 and 3 , the enantiomeric resolution has been achieved via the semioxamazones of ketone 2 .