Absolute Asymmetric Synthesis: The Origin, Control, and Amplification of Chirality

Feringa, Bernard; Delden, Richard A. van

doi:10.1002/(sici)1521-3773(19991203)38:23<3418::aid-anie3418>3.0.co;2-v

Cited by 727 publications

(209 citation statements)

References 90 publications

(113 reference statements)

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“…Irradiation with CPL of a racemic mixture of chiral molecules can selectively enrich one enantiomer up to a small extent, called 'symmetry breaking' 3,4 . It has been speculated that this slight chiral bias might have been amplified via autocatalytic reactions or crystallization processes during the evolutionary process 5 , resulting in homochirality.…”

mentioning

confidence: 99%

Induction and control of supramolecular chirality by light in self-assembled helical nanostructures

et al. 2015

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Evolution of supramolecular chirality from self-assembly of achiral compounds and control over its handedness is closely related to the evolution of life and development of supramolecular materials with desired handedness. Here we report a system where the entire process of induction, control and locking of supramolecular chirality can be manipulated by light. Combination of triphenylamine and diacetylene moieties in the molecular structure allows photoinduced self-assembly of the molecule into helical aggregates in a chlorinated solvent by visible light and covalent fixation of the aggregate via photopolymerization by ultraviolet light, respectively. By using visible circularly polarized light, the supramolecular chirality of the resulting aggregates is selectively and reversibly controlled by its rotational direction, and the desired supramolecular chirality can be arrested by irradiation with ultraviolet circularly polarized light. This methodology opens a route to ward the formation of supramolecular chiral conducting nanostructures from the self-assembly of achiral molecules.

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confidence: 99%

Induction and control of supramolecular chirality by light in self-assembled helical nanostructures

et al. 2015

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“…A hallmark of lifes chemistry is its homochirality [1,[11][12][13][14][15], which is well illustrated by the central molecules of life, namely proteins and nucleic acids. Proteins consist of polypeptide chains made from combinations of 20 different amino acids (primary structure), all exclusively the L-enantiomers.…”

Section: Homochiralitymentioning

confidence: 93%

“…The production of an ee in more general situations is often referred to as absolute enantioselection or physical chiral induction. The subject still attracts much interest and controversy [12,13,15,67]. The considerations of Section 1.3.3 above provide a sound foundation for the critical assessment of physical influences capable of inducing ees, however small.…”

Section: Absolute Enantioselectionmentioning

confidence: 99%

“…The ability of a truly chiral influence to induce absolute asymmetric synthesis in a reaction process at equilibrium may be illustrated by a simple symmetry argument applied to the following unimolecular process [12,13,15,67]. Photochemistry with circularly polarized light is especially favorable because it conforms to Jaegers dictum above.…”

Section: Truly Chiral Influencesmentioning

confidence: 99%

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An Introduction to Chirality at the Nanoscale

Barron

2009

Chirality at the Nanoscale

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“…The use of metallophilic interactions as the driving force has opened up a new strategy for the construction of helical strands of metallo-foldamers that are of immense interest in supramolecular architectures. Chiral supramolecular chemistry has also been of great interest over the last decade, with its profound potential for enantioselective applications , such as chiral separation (64,65), molecular discrimination (66)(67)(68)(69), asymmetric synthesis (70)(71)(72), liquid crystals (73)(74)(75), nonlinear optics (76,77), and so forth. One representative class of chiral moiety is the 1,1-binaphthyls, which have extensive applications in molecular recognition (81)(82)(83)(84), asymmetric catalysis (85), and materials (86).…”

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confidence: 99%

Dynamic scaffold of chiral binaphthol derivatives with the alkynylplatinum(II) terpyridine moiety

Leung

Lam

Yam

2013

Proc. Natl. Acad. Sci. U.S.A.

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Platinum(II)-containing complexes with inherently chiral binaphthol derivatives display a versatile scaffold between random coils and single-turn helical strands, in which the conformational transition is controlled by the Pt···Pt and π−π interactions of alkynylplatinum(II) terpyridine moiety upon solvent and temperature modulation. The bisignate Cotton effect in the circular dichroism spectra is indicative of the cooperative transformation from random coil state to a compact single-turn M-or P-helix. More importantly, as revealed by the appearance of new UV-vis absorption and emission bands during conformational change, the self-assembly of the platinum(II)-containing complex into a helical structure is assisted by the metal···metal and π−π interactions of the alkynylplatinum(II) terpyridine moieties. The folded structure with stabilization via metal···metal and π−π interactions has been supported by density functional theory calculations, which provide insights into the folded geometry of these kind of metallo-foldamers. chirality | luminescence | noncovalent interactions | platinum complex T he photophysical and spectroscopic properties of the d 8 platinum(II) polypyridine system have been extensively studied (1−36) and are pioneered by the works of various groups, such as those of Miskowski and colleagues (1-3), Gray and colleagues (4-6), Lippard and colleagues (7-11), Che and colleagues (12-15), Vogler and colleagues (16), and McMillin and colleagues (17). Such square-planar platinum(II) complexes have been shown to exhibit interesting and intriguing photophysical properties associated with a tendency to form metal···metal and/or π−π stacking interactions (1-17). Most of the studies on these platinum(II) polypyridine systems related to the metal···metal interactions are mainly associated with their rich solid-state polymorphism and are confined to that in the study of solid-state spectroscopy and electronic structures (4,8,14). Corresponding studies in solution are relatively unexplored (8).In view of the relatively small association constants for dimerization or oligomerization found for these compounds in solution, high solubility would be an important prerequisite for them in the preparation of solutions for the study of aggregation in solution. However, poor solubility of the platinum(II) polypyridine system is commonly encountered in solution and limits an extensive study of its aggregation properties in solution.As an extension of our previous work on transition metal alkynyl complexes (37-45), efforts have been made to prepare the first luminescent alkynylplatinum(II) terpyridine system, [Pt(tpy)(C≡CR)] + (20), with improved solubility through the incorporation of strong σ-donating and solubilizing alkynyl ligands into the platinum(II) metal center. Apart from the rich photophysical and luminescence properties, as well as interesting solid-state polymorphism, such complexes exhibit notable color changes and luminescence enhancements as a result of Pt···Pt and π−π stacking interactions that occur from...

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Absolute Asymmetric Synthesis: The Origin, Control, and Amplification of Chirality

Cited by 727 publications

References 90 publications

Induction and control of supramolecular chirality by light in self-assembled helical nanostructures

Induction and control of supramolecular chirality by light in self-assembled helical nanostructures

An Introduction to Chirality at the Nanoscale

Dynamic scaffold of chiral binaphthol derivatives with the alkynylplatinum(II) terpyridine moiety

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