The synthesis and catalytic properties of a new type of enantioselective phase-transfer catalysts, incorporating both the quinuclidinemethanol fragment of Cinchona alkaloids and a 1,1'-binaphthalene moiety, are described. Catalyst ()-(aS,3R,4S,8R,9S)-4 with the quinuclidine fragment attached to C(7') in the major groove of the 1,1'-binaphthalene residue was predicted by computer modeling to be an efficient enantioselective catalyst for the unsymmetric alkylation of 6,7-dichloro-5-methoxy-2-phenylindanone (1; Scheme 1, Fig. 1). Its synthesis involved the selective oxidative cross-coupling of two differently substituted naphthalen-2-ols to afford the asymmetrically substituted 1,1'-binaphthalene derivative ( AE )-17 in high yield ( Scheme 3). Chromatographic optical resolution via formation of diastereoisomeric camphorsulfonyl esters and functional-group manipulation gave access to the 7-bromo-1,1'-binaphthalene derivative (À)-(aS )-11 ( Scheme 4). Nucleophilic addition of lithiated (À)-(aS )-11 to the quinuclidine Weinreb amide ()-(3R,4S,8R )-8 afforded the two ketones (aS,3R,4S,8R )-27 and (aS,3R,4S,8S )-28 as an inseparable mixture of diastereoisomers ( Scheme 6). Stereoselective reduction of this mixture with DIBAL-H (diisobutylaluminum hydride; preferred formation of the C(8)ÀC( 9) erythro-pair of diastereoisomers with 18% de) or with NaBH 4 (preferred formation of the threopair of diastereoisomers with 50% de) afforded the four separable diastereoisomers ()-(aS,3R,4S,8S,9S )-29, ()-(aS,3R,4S,8R,9R )-30, (À)-(aS,3R,4S,8S,9R )-31, and ()-(aS,3R,4S,8R,9S )-32 ( Scheme 6). A detailed conformational analysis, combining 1 H-NMR spectroscopy and molecular-mechanics computations, revealed that the four diastereoisomers displayed distinctly different conformational preferences ( Figs. 2 and3). These novel Cinchona-alkaloid analogs were quaternized to give ()-(aS,3R,4S,8R,9S )-4, ()-(aS,3R,4S,8S,9S )-5, ()-(aS,3R,4S,8R,9R )-6, and (À)-(aS,3R,4S,8S,9R )-7 ( Scheme 7) which were tested as phase-transfer agents in the asymmetric allylation of phenylindanone 1. Without any optimization work, ()-(aS,3R,4S,8R,9S )-4 was found to catalyze the allylation of 1 yielding the predicted enantiomer ()-( S )-3b in 32% ee. The three diastereoisomeric catalysts ()-5, ()-6, and (À)-7 gave access to lower enantioselectivities (6 to 22% ees), which could be rationalized by computer modeling ( Fig. 4).