X-ray structural studies of chiral .beta.-lactam formation from an achiral oxo amide using the chiral crystal environment

Sekine, Akiko; Hori, Kentaro; Ohashi, Yuji; Yagi, Minoru; Toda, Fumio

doi:10.1021/ja00184a045

Cited by 87 publications

(30 citation statements)

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“…Other instances of chiral crystal lattices directing asymmetric syntheses to yield optically active products are found in the 7-ray induced isotactic polymerization of trans-1, 3-pentadiene in an all-trans perhydrotriphenylene crystal lattice (Farina et aL, 1967;Audisio and Silvani, 1976), in the assymmetric photocycloaddition of 1,4-diarylbutadienes to form optically active cyclobutane products (Elgavi et aL, 1973), in the formation of optically active polymers by the photopolymerization of enantiomeric monomer crystals of various p-divinylbenzene derivatives (Addadi et aL, 1975Addadi and Lahav, 1978, 1979a, b, c, 1982Lahav et al, 1976), in the unimolecular di-n--methane type and Norrish Type II photorearrangements of a maleic diester and of a-(3-methyladamantyl)-p-chloroacetophenone, respectively (Evans et aL, 1986) and in the Norrish Type II solid-state photocyclization of the achiral oxo amide, N,N-diisopropylphenylglyoxylamide, into an optically active f~lactam (Toda et aL, 1987;Toda, 1988Sekine et al, 1989). The pertinence of such solid state photoreactions to the origin of chirality on Earth is stressed by several of these authors, and the principles behind such asymmetric syntheses in the crystalline state have been extensively reviewed (Addadi and Lahav, 1979a, b, c;Addadi et al, 1979;Green et al, 1975Green et al, , 1979.…”

Section: Asymmetric Syntheses In Chiral Crystalsmentioning

confidence: 99%

The origin and amplification of biomolecular chirality

Bonner

1991

Origins Life Evol Biosphere

527

370

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Section: Asymmetric Syntheses In Chiral Crystalsmentioning

confidence: 99%

The origin and amplification of biomolecular chirality

Bonner

1991

Origins Life Evol Biosphere

527

370

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“…The title compound was prepared according to a reported method (Toda et al, 1987(Toda et al, ,1997Sekine et al, 1989): chlorination of the phenylglyoxylic acid with thionyl chloride followed by reaction with N-isopropylaniline and triethylamine. Thus, to an ice-cooled solution of N-isopropylaniline The molecular structure of the title compound 1c.…”

Section: Synthesis and Crystallizationmentioning

confidence: 99%

Crystal structure of N-isopropyl-N-(phenyl)phenylglyoxylamide

et al. 2018

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“…The pioneering study of such class of ''absolute'' asymmetric transformations, by Penzien and Schmidt [35], was the gas-solid asymmetric bromination of the nonchiral p, p -dimethyl-chalcone, which crystallizes in an enantiomorphous crystal. Following this study, the details of over 20 such photoinitiated and thermally initiated reactions have been reported [36][37][38][39][40][41][42].…”

Section: ''Absolute'' Asymmetric Polymerization In 3-d Crystalsmentioning

confidence: 99%

“Absolute” Asymmetric Polymerization within Crystalline Architectures: Relevance to the Origin of Homochirality

Weissbuch

Lahav

2012

Materials Science and Technology

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The emergence of the homochiral proteins and nucleic acids, composed from residues of L-amino acids and D-sugars respectively, from the achiral prebiotic world still provides an unsolved conundrum in the field of the origin of life. This mist results from the fundamental symmetry rules as defined, at the end of the nineteenth century, by the Curie principle [1], which states that, '' . . . a physical event cannot have a symmetry lower than that of the event that caused it.''There are two classes of asymmetric transformation, which are in keeping with this symmetry rule. In the first class, chiral reactants are converted, via chemical reactions, into chiral products; in the second class, ''mirror-symmetry'' can be broken spontaneously in either a single or a small number of chemical reactions. In a large number of related independent events, however, the system will preserve its initial nonchiral symmetry. Such class of stochastic asymmetric transformations might have been relevant to chiro-biogenesis, provided the scenario can be accepted that life started in a small number of locations, and that the handedness generated by chance has been amplified and propagated during a competition with heterochiral architectures, such that one of the homochiral architectures has tripped and the other has won the rivalry [2][3][4][5].In this chapter, the second class of stochastic asymmetric synthesis of polymers -referred to as ''absolute'' asymmetric synthesis -and which has been materialized in laboratory experiments, is described. Several successful systems of ''mirror-symmetry breaking'' have been shown to comprise the following steps: spontaneous self-assembly of molecules into crystalline-like supramolecular architectures that create a local homochiral molecular environment exerting asymmetric induction in the ensuing propagation of the polymerization reaction. Farina [6] coined the term ''through-space'' asymmetric transformations in order to distinguish them from the common ''through-bond'' reactions.Here, attention is confined especially to the asymmetric transformations of achiral monomers within crystalline or quasi-crystalline architectures. In particular, the early studies of asymmetric polymerizations performed within enantiomorphous

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X-ray structural studies of chiral .beta.-lactam formation from an achiral oxo amide using the chiral crystal environment

Cited by 87 publications

References 0 publications

The origin and amplification of biomolecular chirality

The origin and amplification of biomolecular chirality

Crystal structure of N-isopropyl-N-(phenyl)phenylglyoxylamide

“Absolute” Asymmetric Polymerization within Crystalline Architectures: Relevance to the Origin of Homochirality

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