Enantioselective epoxidation of α,β-unsaturated ketones using polymer-supported lanthanoid–BINOL complexes

Synthesis, Characterization and Catalytic Properties of Chiral BINOL Functionalized Mesoporous Silicas for Enantioselective Morita-Baylis-Hillman Reaction

“…FT-IR spectra of chiral BINOL functionalized silicas 3a, 3b, 3c and 3d show two characteristic peaks of asymmetric bending vibration of C-H in binaphthyl group [27]. In addition, the main bands at 1068 cm -1 and around 801 cm -1 are associated with the asymmetric and symmetric stretching vibrations of Si-O-Si.…”

“…Compounds 1a, 1b, 1c and 1d were obtained according to the references [23,27,34] from (S)-BINOL and bromides of (S)-BINOL through only three steps including protection by MOMCl (CH 3 OCH 2 Cl), carbonylation at its 3, 3,3 0 , 6 and 6,6 0 positions and reducation to hydroxylmethyl groups, respectively. The products 2a, 2b, 2c and 2d can be purified by flash column chromatography, with the following corresponding yields: 84%, 62%, 82% and 67%.…”

“…Specifically, chiral BINOLs were accepted as optimal candidates for the asymmetric Morita-Baylis-Hillman reaction [18] and asymmetric allylboration of ketones [19,20] as chiral Brønsted acids even though they have been widely used in metal-centered Lewis acid catalysts [21]. Various supports such as organic polymers [22][23][24][25][26][27][28][29][30], inorganic materials [31][32][33], dendrimers [34], have been investigated to immobilize BINOLs as metal-centered Lewis acid catalysts in a lot of asymmetric catalytic reactions. Meanwhile, one organosilane derivative of chiral BINOL was post-grafted onto ordered mesoporous silicas MCM-41 [35] and SBA-15 [36] by Abdi and coworkers to catalyze asymmetric nitroaldol reaction [37] and enantioselective addition of diethylzinc to aldehydes [38] centered with different metal ions.…”

Chiral rings from BINOL dicarboxylic acids and alkane ditin(IV) linkers

“…Importantly, both enantiomers ( R and S forms) of BINOL are readily available and inexpensive. The incorporation of chiral BINOL into MOFs can prepare systems useful for asymmetric synthesis and chiral catalytic processes (Burk et al , 1991 ;Kumaraswamy et al , 2001 ;Pandiaraju et al , 2001 ;Trotta et al , 2002 ;Jayaprakash et al , 2003 ;Shibasaki and Matsunaga , 2006 ).…”

Synthesis of Poly(Ethylene Glycol)–Supported (R)-BINOL Derivatives and Their First Application in Enantioselective Mukaiyama Aldol Reactions

“…On the other hand, among the large number of ligands being subjected to asymmetric syntheses, C 2 -symmetric 1,1 0 -binaphthyl-2,2 0 -diol (abbreviated as BINOL) and its derivatives have occupied a prominent position. [3] Recently, a number of immobilized soluble or insoluble BINOL derivatives have been synthesized, and the resulting polymersupported BINOL complexes were applied in asymmetric transformations such as aza Diels-Alder reactions, [4] additions of diethyl zinc to aldehydes, [5] carbonyl-ene reactions, [6] sulfoxidation reactions, [5d, 6,7] Strecker-type reactions, [8] Michael additions, [9] 1,3-dipolar cycloadditions, [5d] epoxidations, [9,10] and other transformations. [11] To the best of our knowledge, at present only a few contributions have been reported that deal with soluble PEG-supported catalysts for asymmetric Mukaiyama aldol reactions.…”