Tunable chirality

Asymmetric catalytic hydrogenation is unquestionably one of the most significant transformations for academic and industrial-scale synthesis. The development of tunable chiral phosphorous ligands, and of their ability to control enantioselectivity and reactivity, has allowed asymmetric catalytic hydrogenation to become a reaction of unparalleled versatility and synthetic utility. This is exemplified in the ability to prepare en-antiomerically enriched intermediates from prochiral olefins, ketones, and imines through asymmetric hydrogenation, which has been exploited in industry for the synthesis of enantiomerically enriched drugs and fine chemicals. 

Matsui T, Ozaki M, Yoshino K (2004) Tunable photonic defect modes in a cholesteric liquid crystal induced by optical deformation of helix. Phys Rev E 69 061715 Yoshida H, Lee CH, Fujii A, Ozaki M (2007) Tunable chiral photonic defect modes in locally polymerized cholesteric liquid crystals. Mol Cryst Liq Cryst 477 255... 

F. Vicentini and L.-C. Chien, Tunable chiral materials for multicolor reflective cholesteric displays, Liq. 

The concept of tunable chiral thiourea based organocatalysts, useful for a wide variety of asymmetric reactions, was invented by Jacobsen in 1999 and has been extensively reviewed over the last few years. They have been... 

Abstract The unique and readily tunable electronic and spatial characteristics of ferrocenes have been widely exploited in the field of asymmetric catalysis. The ferrocene moiety is not just an innocent steric element to create a three-dimensional chiral catalyst enviromnent. Instead, the Fe center can influence the catalytic process by electronic interaction with the catalytic site, if the latter is directly coimected to the sandwich core. Of increasing importance are also half sandwich complexes in which Fe is acting as a mild Lewis acid. Like ferrocene, half sandwich complexes are often relatively robust and readily accessible. This chapter highlights recent applications of ferrocene and half sandwich complexes in which the Fe center is essential for catalytic applications. 

Currently, it is fair to say that asymmetric synthesis using chiral quaternary ammonium fluorides remains an underdeveloped field, and the various useful stereoselective carbon-carbon bond-forming processes described in this chapter are only the start of an exploration of the vast synthetic potential of this process, particularly when combined with current knowledge of organosilicon chemistry. It seems that the key issue to be addressed is the rational molecular design of chiral quaternary ammonium cations with appropriate steric and electronic properties. These are expected to be readily tunable to impart not only a sufficient reactivity but also an ideal chiral environment to the requisite nucleophile involved in a desired chemical transformation. Clearly, the continuous accumulation of information related to the structure of fluoride salts and their reactivity and selectivity should create a solid basis for this field, offering - in time - a unique yet reliable tool for sophisticated bond construction events with rigorous stereocontrol, under mild conditions. 

Using an elegant approach, Che et al. prepared chiral mesoporous silica using bio-inspired surfactants [63]. The trimethylammonium group of the quaternary amine used as a surfactant in the synthesis of MCM-41 (CTAB) was replaced by L-alanine. The chirality of the amino acid in the polar head of the surfactant induces chirality in the micelle used as template (see Figure 3.15). This simple modification in the surfactant allowed the preparation of the first chiral mesoporous silica with tunable pore size and ordered porosity. A key step in this synthesis is the transfer of the chirality from the surfactant to the solid, which was accomplished by electrostatic interaction between the terminal amino acid and the... 

A planar chiral naphthalenediimide cyclophane (39) and its derivatives were prepared for their tunable intramolecular FRET properties. The enantiomeric enrichment of cyclophane 39 was accomplished by chiral HPLC (on a Daicel IA column) and the CD spectra of enantiomeric 39 were reported (Fig. 9) [51]. 

Gabutti S, Schaffner S, Neuburger M, Fischer M, Schafer G, Mayor M (2009) Planar chiral asymmetric naphthalenediimide cyclophanes synthesis, characterization and tunable FRET properties. Org Biomol Chem 7 3222-3229... 

Crown ether research, as it stands today, does not seem to be suffering from any age crisis. On the contrary, it appears that many new developments are underway. Judging from the most recent accounts that have appeared in the literature, there is plenty of room in the years to come for further investigations in the field of polymer- and dendrimer-based new tunable materials, as well as in the construction of nanosize molecular devices. Furthermore, the never-ending quest for chirally discriminating host molecules and increasingly sensitive and selective sensors for analytes of both biomedical and environmental interest calls for additional studies on crown ethers. 

As mentioned in the previous section, nowadays, readily available and inexpensive cinchona alkaloids with pseudoenantiomeric forms, such as quinine and quinidine or cinchonine and cinchonidine, are among the most privileged chirality inducers in the area of asymmetric catalysis. The key feature responsible for their successful utility in catalysis is that they possess diverse chiral skeletons and are easily tunable for diverse types of reactions (Figure 1.2). The presence of the 1,2-aminoalcohol subunit containing the highly basic and bulky quinuclidine, which complements the proximal Lewis acidic hydroxyl function, is primarily responsible for their catalytic activity. 

The naturally occurring cinchona alkaloids (Figure 8.1), as described in other chapters of this book, have proven to be powerful organocatalysts in most major chemical reactions. They possess diverse chiral skeletons and are easily tunable for diverse catalytic reactions through different mechanisms, which make them privileged organocatalysts. The vast synthetic potential of cinchona alkaloids and their derivatives in the asymmetric nucleophilic addition of prochiral C=0 and C=N bonds has also been well demonstrated over the last decade. 

Cinchona alkaloids are readily available natural chiral compounds and have a long history to be utilized as organocatalysts in asymmetric catalysis [3, 4]. They are multifunctional, tunable, and more importantly, they could promote a diversity of reactions through different catalytic mechanisms, which make them privileged catalysts in organocatalysis. In this chapter, the applications of cinchona alkaloids and their derivatives for asymmetric cydoaddition reactions after 2000, especially for the construction of a variety of five- and six-membered cyclic compounds, are discussed. 

Figure 4.15 Chiral tunable dendritic diamine ligands.

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