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Kleine Ringe, 90. Peralkyl‐substituierte Tetrahedrane
Author(s) -
Maier Günther,
Fleischer Frank,
Kalinowski HansOtto
Publication year - 1994
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.199519950124
Subject(s) - chemistry , intramolecular force , diazo , carbene , cycloaddition , molecule , photodissociation , thermal decomposition , photochemistry , stereochemistry , medicinal chemistry , organic chemistry , catalysis
Small Rings, 90. – Peralkyl‐Substituted Tetrahedranes Photolysis of the diazo compounds 4a, b generates adaman‐tyltri‐ tert ‐butyltetrahedrane ( 9a ) and tri‐ tert ‐butylisopropyltetrahedrane ( 9b ), and the corresponding cyclobutadienes 10a, b . In contrast to tetrahedrane 9a , which results from an intramolecular addition in carbene 7a and also from photoisomerization of cyclobutadiene 10a , the only source for tetrahedrane 9b is the cheletropic cycloaddition of the carbenic center to the cyclopropene double bond in the photochemically produced carbene 7b . Tetrahedrane 9b is remarkable in its kinetic and thermal instability, which is caused by the reduced „corset effect” in this compound. An additional access to this tetrahedrane is possible via the diazomethanes 34A and 34B . The pyridazines 17b and 41 , which are formed by thermolysis of the diazo compounds 4b, 34A and 34B lead to the azetes 19 and 43 . Last but not least 17b and 41 are interesting molecules themselves because of their inherent chirality.