Towards the planning and execution of an "absolute" asymmetric synthesis of chiral dimers and polymers with quantitative enantiomeric yield

Addadi, Lia; Lahav, Meir

doi:10.1351/pac197951061269

Cited by 76 publications

(36 citation statements)

References 26 publications

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“…This was achieved in the following way. Molecular dienes were 'engineered' to pack in chiral crystals (Addadi & Lahav, 1979;Addadi, van Mil & Lahav, 1982;van Mil, Addadi, Gati & Lahav, 1981, in which the molecules are stacked by translation such that the neighboring C..-C double bonds are in appropriate proximity for photodimerization (Scheme 8). UV irradiation of a single crystal yields dimers, trimers and oligomeric products of a single chirality Pr or Ps, dependent upon the chirality of the starting crystal.…”

Section: Amplification Of Chirality By Crystallization With Chiral Admentioning

confidence: 99%

Understanding and control of nucleation, growth, habit, dissolution and structure of two- and three-dimensional crystals using `tailor-made' auxiliaries

Weissbuch¹,

Popovitz‐Biro²,

Lahav³

et al. 1995

Acta Crystallogr B Struct Sci

Self Cite

332

288

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Tailor-made auxiliaries for the control of nucleation and growth of molecular crystals may be classified into two broad categories: inhibitors and promoters. Tailor-made inhibitors of crystal growth can be used for a variety of purposes, which include morphological engineering and etching, reduction of crystal symmetry, assignment of absolute structure of chiral molecules and polar crystals, elucidation of the effect of solvent on crystal growth, and crystallization of a desired polymorph. As for crystal growth promoters, monolayers of amphiphilic molecules on water have been used to induce the growth of a variety of three-dimensional crystals at the monolayer-solution interface by means of structural match, molecular complementarity or electrostatic interaction. A particular focus is made on the induced nucleation of ice by mono- © 1995 International Union of Crystallography Printed in Great Britain -all fights reserved layers of water-insoluble aliphatic alcohols. The twodimensional crystalline structures of such monolayers have been studied by grazing incidence X-ray diffraction. It has become possible to monitor, by this method, the growth, dissolution and structure of self-aggregated crystalline monolayers, and indeed multilayers, affected by the interaction of solvent molecules in the aqueous subphase with the amphiphilic headgroups, and by the use of tailor-made amphiphilic additives.

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Section: Amplification Of Chirality By Crystallization With Chiral Admentioning

confidence: 99%

Understanding and control of nucleation, growth, habit, dissolution and structure of two- and three-dimensional crystals using `tailor-made' auxiliaries

Weissbuch¹,

Popovitz‐Biro²,

Lahav³

et al. 1995

Acta Crystallogr B Struct Sci

Self Cite

332

288

View full text Add to dashboard Cite

show abstract

“…It gained an identity of sorts by the 1980s, attracting crystallographers, solid-state chemists, theoreticians, and inorganic chemists to its ranks. [4][5][6] Today, the subject covers a community of at least 150 independent research groups, with two specialist journals-Crystal Growth and Design from the ACS and CrystEngComm from the RSC-and even a dedicated webpage and a Wikipedia site maintained by the latter society. A working definition of crystal engineering, which I supplied in my 1989 book, [1] namely that it is "the understanding of intermolecular interactions in the context of crystal packing and in the utilisation of such understanding in the design of new solids with desired physical and chemical properties", seems to have stood the test of time, and the subject today includes three distinct activities, which form a continuous sequence: 1) the study of intermolecular interactions; 2) the study of packing modes, in the context of these interactions and with the aim of defining a design strategy; and 3) the study of crystal properties and their fine-tuning with deliberate variations in the packing.…”

Section: Introductionmentioning

confidence: 99%

Crystal Engineering: A Holistic View

Desiraju¹

2007

Angew Chem Int Ed

1,355

866

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Crystal engineering, the design of molecular solids, is the synthesis of functional solid-state structures from neutral or ionic building blocks, using intermolecular interactions in the design strategy. Hydrogen bonds, coordination bonds, and other less directed interactions define substructural patterns, referred to in the literature as supramolecular synthons and secondary building units. Crystal engineering has considerable overlap with supramolecular chemistry, X-ray crystallography, materials science, and solid-state chemistry and yet it is a distinct discipline in itself. The subject goes beyond the traditional divisions of organic, inorganic, and physical chemistry, and this makes for a very eclectic blend of ideas and techniques. The purpose of this Review is to highlight some current challenges in this rapidly evolving subject. Among the topics discussed are the nature of intermolecular interactions and their role in crystal design, the sometimes diverging perceptions of the geometrical and chemical models for a molecular crystal, the relationship of these models to polymorphism, knowledge-based computational prediction of crystal structures, and efforts at mapping the pathway of the crystallization reaction.

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“…Keywords: amino acids · homochirality · mass spectrometry · oligophenylalanine · solid-state reactions · topochemistry from the 2 p-2 p photopolycycloaddition reactions of diethylenes, [14,15] di-and triacetylenes, [16] butadienes, [17][18][19] and some organometallic monomers [20,21] that have been demonstrated to undergo topochemical reactions, polymerization of most other monomers yields only atactic polymers. Therefore, the generation of homochiral polypeptides through heterogeneous polymerization reactions in three-dimensional crystals as a possible reaction pathway was not regarded as a viable scenario.…”

Section: Introductionmentioning

confidence: 99%

Homochiral Oligopeptides Generated by Induced “Mirror Symmetry Breaking” Lattice‐Controlled Polymerizations in Racemic Crystals of Phenylalanine N‐Carboxyanhydride

Nery

Bolbach

Weissbuch

et al. 2005

Chemistry A European J

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The formation of diastereoisomeric libraries of oligopeptides through the heterogeneous polymerization of racemic crystals of phenylalanine N-carboxyanhydride (PheNCA) is reported. The diastereoisomeric compositions of the oligopeptides formed on polymerization of (R,S) crystals incorporating the deuterium-tagged S enantiomer were determined by MALDI-TOF mass spectrometry. The racemic mixtures of the oligopeptides longer than pentamers are represented primarily by diastereoisomers of homochiral sequence and with peptides containing only one heterochiral repeating unit. A mechanism comprising the following three sequential steps to account for this unusual observation is proposed: 1) formation of dimers and trimers at a partially damaged liquid/solid interface, 2) chain propagation that takes place within the bulk of the crystal through a lattice-controlled "zipper-like" mechanism between homochiral molecules arranged in a head-to-tail motif to yield crystalline antiparallel beta-sheets of alternating oligopeptide chains of homochiral sequence of opposite handedness, and 3) enantiomeric cross-inhibition that results in chain termination. Induced desymmetrization of the racemic mixtures of the formed peptides was achieved by the polymerization of the mixed quasi-racemic crystals of (R)-PheNCA, ((S)-PheNCA), and (S)-ThieNCA (3-(2-thienyl)-alanine N-carboxyanhydride) of various compositions. These experiments resulted in the formation of nonracemic libraries of oligopeptides composed of homochiral chains of (R)-Phe and copolymers of randomly distributed (S)-Phe and (S)-Thie sequences. From these findings, we propose a stochastic model for the generation of libraries of nonracemic mixtures of oligopeptides from the polymerization of host (R,S)-PheNCA with racemic mixtures of other guest NCA amino acids dissolved in limited quantities in the crystal.

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Towards the planning and execution of an "absolute" asymmetric synthesis of chiral dimers and polymers with quantitative enantiomeric yield

Cited by 76 publications

References 26 publications

Understanding and control of nucleation, growth, habit, dissolution and structure of two- and three-dimensional crystals using `tailor-made' auxiliaries

Understanding and control of nucleation, growth, habit, dissolution and structure of two- and three-dimensional crystals using `tailor-made' auxiliaries

Crystal Engineering: A Holistic View

Homochiral Oligopeptides Generated by Induced “Mirror Symmetry Breaking” Lattice‐Controlled Polymerizations in Racemic Crystals of Phenylalanine N‐Carboxyanhydride

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