TY - JOUR
T1 - Synthesis of functionalized chiral carbocyclic cleft molecules complementary to Troger's base derivatives
AU - Kimber, Marc C.
AU - Try, Andrew C.
AU - Painter, Leoni
AU - Harding, Margaret M.
AU - Turner, Peter
PY - 2000/5/19
Y1 - 2000/5/19
N2 - The synthesis of optically pure functionalized cleft molecules derived from dibenzobicyclo[b,f][3.3.1]nona-5a,6a-diene-6,12-dione is reported. These clefts are reminiscent of Troger's base but contain clefts with different dimensions and additional carbonyl (or alcohol) groups that may be utilized in molecular recognition studies. The 2,8-dimethyl and 2,8-dibromo derivatives were synthesized via an intramolecular Friedel-Crafts acylation and were resolved by chiral HPLC. The 2,8-dinitro derivative was prepared by regiospecific nitration of dibenzobicyclo[b,f][3.3.1]nona-5a,6a-diene-6,12- dione. The dibromo and dinitro derivatives allow direct access to a range of functionalized molecular clefts. Palladium-catalyzed coupling of the dibromo derivative afforded the disubstituted phenyl, anisole, and acetylene derivatives, while reduction of the dinitro derivative and acetylation provided amino-dione and amide-hydroxyl derivatives. X-ray crystal structures of the dimethyl 12, dibromo 13, di(p-methoxyphenyl) 16, dinitro 18, and dimethyl dinitro 22 derivatives show cleft angles between the planes between the aromatic rings of 84-104°. The synthetic route, structural features, and potential for molecular recognition studies of this class of clefts are compared with those of the more widely studied Troger's base cleft molecules.
AB - The synthesis of optically pure functionalized cleft molecules derived from dibenzobicyclo[b,f][3.3.1]nona-5a,6a-diene-6,12-dione is reported. These clefts are reminiscent of Troger's base but contain clefts with different dimensions and additional carbonyl (or alcohol) groups that may be utilized in molecular recognition studies. The 2,8-dimethyl and 2,8-dibromo derivatives were synthesized via an intramolecular Friedel-Crafts acylation and were resolved by chiral HPLC. The 2,8-dinitro derivative was prepared by regiospecific nitration of dibenzobicyclo[b,f][3.3.1]nona-5a,6a-diene-6,12- dione. The dibromo and dinitro derivatives allow direct access to a range of functionalized molecular clefts. Palladium-catalyzed coupling of the dibromo derivative afforded the disubstituted phenyl, anisole, and acetylene derivatives, while reduction of the dinitro derivative and acetylation provided amino-dione and amide-hydroxyl derivatives. X-ray crystal structures of the dimethyl 12, dibromo 13, di(p-methoxyphenyl) 16, dinitro 18, and dimethyl dinitro 22 derivatives show cleft angles between the planes between the aromatic rings of 84-104°. The synthetic route, structural features, and potential for molecular recognition studies of this class of clefts are compared with those of the more widely studied Troger's base cleft molecules.
UR - http://www.scopus.com/inward/record.url?scp=0034685996&partnerID=8YFLogxK
U2 - 10.1021/jo991741p
DO - 10.1021/jo991741p
M3 - Article
SN - 0022-3263
VL - 65
SP - 3042
EP - 3046
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
IS - 10
ER -