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The Pagodane Route to Dodecahedranes Scope and Limitation of the Dehydrocyclization Stratagem
Author(s) -
Lutz Georg,
Pinkos Rolf,
Murty Bulusu A. R. C.,
Spurr Paul R.,
Fessner WolfDieter,
Wörth Jürgen,
Fritz Hans,
Knothe Lothar,
Prinzbach Horst
Publication year - 1992
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19921250729
Subject(s) - chemistry , carbene , substituent , yield (engineering) , alkyl , medicinal chemistry , alkylation , closure (psychology) , catalysis , ring (chemistry) , stereochemistry , insertion reaction , double bond , organic chemistry , market economy , materials science , economics , metallurgy
The stepwise route B from pagodanes to dodecahedranes was completed by double catalytic dehydrocyclization of saturated (alkylated) bisseco precursor substrates ( 2, 3, 5, 16 ). Based on pagodane, dodecahedranes ( 9, 10, 13, 14, 17 ) were obtained in up to 53% yield. Transannular C,C bond formation at the bisseco stage and partial (C–alkyl) or total (C–OR, C–CO 2 R) removal of substituent groups under the necessarily forcing reaction conditions constituted preparative limitations. Attempts at alternative ring closure methodologies (homo‐Norrish type II, homoenolization, carbene insertion) have remained unsuccessful.