BINAP dendritic

BINAP core-functionalized dendrimers were synthesized by Fan et al. (36), via condensation of Frechet s polybenzyl ether dendritic wedges to 5,5 -diamino-BINAP (26—28). The various generations of BINAP core-functionalized dendrimers were tested in the ruthenium-catalyzed asymmetric hydrogenation of 2-[p-(2-methyl-propyl)phenyl]acrylic acid in the presence of 80 bar H2 pressure and in a 1 1 (v/v) methanol/toluene mixture. As later generations of the in situ prepared cymeneruthe-nium chloride dendritic catalysts were used, higher activities were observed (TOF values were 6.5, 8.3, and 214 h respectively). Relative to those of the BINAP... 

Since the pioneering studies of asymmetric catalysis with core-functionalized dendrimers reported by Brunner (88) and Bolm (89), several noteworthy investigations have been described in this field. Some examples of the dendritic effects observed in enantioselective catalysis with dendrimers having active sites in the core were discussed in Section II, such as the catalytic experiments with TADDOL-cored dendrimers described by Seebach et al. (59) the asymmetric addition of Et2Zn to aldehydes catalyzed by core-functionalized phenylacetylene-containing dendrimers reported by Hu et al (42)-, the asymmetric hydrogenation investigations with (R)-BINAP core-functionalized dendrimers synthesized by Fan et al. (36) or the results... 

Two interesting reports by Chan and co-workers of dendritic core-functionalized Ru-BINAP (BINAP = 2,2/-bis(diphenylphosphino)-l,l/-binaphthyl) catalysts, which were employed in asymmetric hydrogenations and which were fully recoverable, have appeared recently [40,41]. In particular, such dendrimers containing long alkyl chains in the periphery were synthesized and... 

In a related approach, Fan et al. synthesized a series of dendritic BINAP-Ru/chiral diamine ((R,R)-l,2-diphenylethylenediamine DPEN) catalysts for the asymmetric hydrogenation of various simple aryl ketones (Fig. 15) [42]. The resulting systems displayed high catalytic activity and enantioselectivity and allowed facile catalyst recycling. In the case of 1-acetonaphthone and... 

Fig. 15 BINAP ligand functionalized with poly(aryl ether) dendritic wedges...

The same group also developed optically active dendronized polymeric BINAP ligands (see also Sect. 5) as a new type of macromolecular chiral catalyst for asymmetric hydrogenation. They could be synthesized by condensation of 5,5 -diamino-BINAP with dendritic dicarboxylic acid monomers (Scheme 5) [44],... 

These polymeric Ru(BINAP) catalysts exhibited high catalytic activity and enantioselectivity (up to 92%) in the hydrogenation of simple aryl ketones, which is very similar to the results obtained with the corresponding parent Ru(BINAP) as well as the Ru(BINAP)-cored dendrimers referred to above. Unsurprisingly, they found that the pendant dendritic wedges have a major impact on the solubility and the catalytic properties of the polymeric catalysts, which could be easily recovered from the reaction mixture by simple precipitation. 

Chiral dendritic catalysts 194 derived from BINAP was prepared and used for the asymmetric hydrogenation of quinolines (Scheme 3.63) [126]. The corresponding cyclic amine products were obtained with high enantioselectivities up to 93% ee. The dendritic catalyst showed excellent catalytic activities (TOP up to 3450h" ) and productivities (TON up to 43 000). The dendritic catalyst was recovered by precipitation and filtration and reused at least six times, with similar enantioselectivity. 

Figure 4.5 Chiral dendritic ruthenium catalysts containing BINAP- and DPEN-cored dendrimer ligands.

Very recently, Fan et al. [13] reported on the use of a water-soluble PEO-substitut-ed first- and second-generation Frechet-type dendrimer with a chiral BINOL (1,1 -bi-2-naphthol) unit in catalysis. The enantiomeric excess in asymmetric hydrogenation of 2-[p-(2-methylpropyl)phenyl]acrylic acid with [RuCl(BINAP)(cymene)]Cl in an aqueous system was reported to increase upon addition of the dendritic... 

Dendrimer based-BINAP polymers have been prepared from 124. A series of soluble dendritic mono-BINAP ligands with Frechet-type polyether wedges like 127 and dendritic poly-BlNAP ligands like 128 have been reported Ruthenium complexes of both classes of dendrimer were prepared and found to be comparable both in catalytic activity and enatioselectivity as homogeneous BINAP analogs in asymmetric hydrogenation reactions. 

The first reported example using macromolecule-supported catalysts in latent biphasic systems was work by Chan s group that employed a dendrimer-bound BINAP 127 that was used to form a chiral ruthenium hydrogenation catalyst [164]. The dendritic Ru-BINAP complex formed from the reaction of [RuCl2(benzene)2]2 and 127 was successfully used in four cycles in the hydrogenation of 2-phenylacrylic acid (Eq. 65) in a 1 1 (vol/vol) ethanol/hexane mixture. Addition of 2.5 vol% water to this mixture produced a biphasic mixture where >99% of the dendritic catalyst was in the hexane phase. Addition of a fresh ethanolic substrate solution to this hexane phase produced another miscible solution of catalyst and substrate. The second and subsequent cycles of hydrogenation carried out in this manner led to consistent conversions of substrate with synthetic yields of >91% with e.e. values of 90%. 

Pan et al. give an extensive review of immobilized asymmetric catalysts according to reaction classes and the land of support [9]. Saluzzo and Lemaire reviewed the use of polymer-supported BINAP for hydrogenation and hydrogen-transfer reduction with diamines or amino alcohols, respectively [10]. The immobilization and recycling of chiral catalysts was the topic of a recent book [11]. Dendritic catalysts... 

Figure 4.19 Dendritic BINAP ligands for the Ir-catalyzed asymmetric hydrogenation of quinoline derivatives.

Figure 4.20 Dendritic BiNAP with core—shell structure for the Ru-catalyzed asymmetric hydrogenation.

Figure 4.21 Dendritic BINAP with core-shell structure for the thermomorphic asymmetric hydrogenation.

---