title: Unusual traits of cis and trans-2,3-dibromo-1,1-dimethylindane on the way from 1,1-dimethylindene to 2-bromo-, 3-bromo-, and 2,3-dibromo-1,1-dimethylindene.
abstract: Do not rely on the widely accepted rule that vicinal, sp(3)-positioned protons in cyclopentene moieties should always have more positive (3) J NMR coupling constants for the cis than for the trans arrangement: Unrecognized exceptions might misguide one to wrong stereochemical assignments and thence to erroneous mechanistic conclusions. We show here that two structurally innocent-looking 2,3-dibromo-1,1-dimethylindanes violate the rule by means of their values of (3) J(cis) = 6.1 Hz and (3) J(trans) = 8.4 Hz. The stereoselective formation of the trans diastereomer from 1,1-dimethylindene was improved with the tribromide anion (Br3 (-)) as the brominating agent in place of elemental bromine; the ensuing, regiospecific HBr elimination afforded 3-bromo-1,1-dimethylindene. The addition of elemental bromine to the latter compound, followed by thermal HBr elimination, furnished 2,3-dibromo-1,1-dimethylindene, whose Br/Li interchange reaction, precipitation, and subsequent protolysis yielded only 2-bromo-1,1-dimethylindene.
authors: Department Chemie, Ludwig-Maximilians-Universität München, Butenandtstrasse 5-13 (Haus F), 81377 München, Germany.
authors: Rudolf
authors: R
authors: Knorr
authors: Department Chemie, Ludwig-Maximilians-Universität München, Butenandtstrasse 5-13 (Haus F), 81377 München, Germany.
authors: David S
authors: DS
authors: Stephenson
authors: Department Chemie, Ludwig-Maximilians-Universität München, Butenandtstrasse 5-13 (Haus F), 81377 München, Germany.
authors: Ernst
authors: E
authors: Lattke
authors: Department Chemie, Ludwig-Maximilians-Universität München, Butenandtstrasse 5-13 (Haus F), 81377 München, Germany.
authors: Petra
authors: P
authors: Böhrer
authors: Department Chemie, Ludwig-Maximilians-Universität München, Butenandtstrasse 5-13 (Haus F), 81377 München, Germany.
authors: Jakob
authors: J
authors: Ruhdorfer
keywords: NMR couplings; base-free dehydrobromination; cis/trans stereochemistry; five-membered ring conformation; indenes