Enantioselective CC Bond Formation as a Result of the Oriented Prochirality of an Achiral Aldehyde at the Single‐Crystal Face upon Treatment with a Dialkyl Zinc Vapor

Kawasaki, Tsuneomi; Kamimura, Sayaka; Amihara, Ai; Suzuki, Kenta; Soai, Kenso

doi:10.1002/anie.201102031

Cited by 38 publications

(27 citation statements)

References 52 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Some achiral organic compounds form achiral crystals with enantiotopic faces. A crystal of 2‐( tert ‐butyldimethylsilylethynyl)pyrimidine‐5‐carbaldehyde 4 is an achiral crystal ( P –1) that has enantiotopic faces (Figure ) . When one of these, the Re face, was exposed to the vapor of i ‐Pr 2 Zn, pyrimidyl alkanol ( R )‐ 3 was obtained.…”

Section: The Origins Of Homochirality Examined By Asymmetric Autocatamentioning

confidence: 99%

The Origins of Homochirality Examined by Using Asymmetric Autocatalysis

Soai

Kawasaki

Matsumoto

2014

The Chemical Record

Self Cite

View full text Add to dashboard Cite

Pyrimidyl alkanol was found to act as an asymmetric autocatalyst in the enantioselective addition of diisopropylzinc to pyrimidine-5-carbaldehyde. Asymmetric autocatalysis of 2-alkynylpyrimidyl alkanol with an extremely low enantiomeric excess (ca. 0.00005% ee) exhibits enormous asymmetric amplification to afford the same compound with >99.5% ee. This asymmetric autocatalysis with amplification of ee has been employed to examine the validity of proposed theories of the origins of homochirality. Circularly polarized light, quartz, sodium chlorate, cinnabar, chiral organic crystals and spontaneous absolute asymmetric synthesis were considered as possible candidates for the origin of chirality; each could act as a chiral source in asymmetric autocatalysis. Asymmetric autocatalysis can discriminate the isotope chirality arising from the small difference between carbon (carbon-13/carbon-12) and hydrogen (D/H) isotopes. Cryptochiral compounds were also discriminated by asymmetric autocatalysis.

show abstract

Section: The Origins Of Homochirality Examined By Asymmetric Autocatamentioning

confidence: 99%

The Origins of Homochirality Examined by Using Asymmetric Autocatalysis

Soai

Kawasaki

Matsumoto

2014

The Chemical Record

Self Cite

View full text Add to dashboard Cite

show abstract

“…Very recently, Kawasaki et al28 reported the application of the same concept for the triggering the autocatalytic Soai reaction. When a single crystal of the aldehyde was exposed to i Pr 2 Zn vapor, while having blocked one of the enantoselective {001} faces by embedding into a resin, the enantioselective isopropylation proceeded to afford a chiral 5‐pyrimidyl‐alkanol with the absolute configuration corresponding to the orientation of the achiral aldehyde, Figure 17.…”

Section: “Absolute” Asymmetric Synthesis With Achiral Crystalsmentioning

confidence: 99%

Achiral Organic, Inorganic, and Metal Crystals as Auxiliaries for Asymmetric Transformations

Weissbuch¹,

Leiserowitz²,

Lahav³

2011

Israel Journal of Chemistry

View full text Add to dashboard Cite

The use of achiral crystalline architectures as intermediate auxiliaries for the performance of “absolute” asymmetric transformations is reviewed. Such architectures are delineated, in some cases, by pairs of homochiral surfaces of opposite handedness. This phenomenon is more common among organic crystals that frequently appear in triclinic, monoclinic, orthorhombic, or tetragonal space groups. Consequently, the chiral surfaces of such crystals have been shown to display enantiomeric recognition for molecules of the environment, a process that has been instrumental in the conversion of achiral host crystals into enantiomorphous solid‐solutions, for a successful performance of “absolute” asymmetric transformations and for the control of crystal polymorphism. Mixed crystals of reduced symmetry display properties such as second harmonic generation or pyroelectricity. On the other hand, achiral faces delineate metals, which crystallize in cubic space‐groups of high symmetry. However, by slicing such crystals in particular directions, they might express homochiral high Miller index faces that contain homochiral kink sites, which have been successfully exploited in electrochemical separations of sugars and for the resolution of enantiomers by enantioselective desorption. Representative examples of each class of materials are described.

show abstract

“…[1n,o, 2] Although chiral inorganic minerals have been considered to be an origin of chirality, achiral natural minerals with an enantiotopic surface have rarely been considered as an origin of chirality. [13] Gypsum is a common mineral that has been used in a wide range of applications, including materials for sculpture, plasterboard in buildings, and plaster casts for medical use. Certain metal surfaces, such as artificially cut Cu(643), become enantiotopic, and the enantiomer-selective decomposition of chiral compounds have been reported.…”

mentioning

confidence: 99%

Achiral Inorganic Gypsum Acts as an Origin of Chirality through Its Enantiotopic Surface in Conjunction with Asymmetric Autocatalysis

et al. 2016

Self Cite

View full text Add to dashboard Cite

Achiral inorganic gypsum (CaSO 4 ·2 H 2 O) triggers the asymmetric autocatalysis of pyrimidyl alkanol on its twodimensional enantiotopic faces to give highly enantioenriched alkanol products with absolute configurations corresponding to the respective enantiotopic surfaces. This is the first example of highly enantioselective synthesis on the enantiotopic surface of an achiral mineral.The origins of the homochirality of biological compounds such as l-amino acids and d-sugars have been the subject of great interest in chemistry, biology, physics, astrobiology, and studies on the origin of life. [1] There have been several theories proposed for the origins of the chirality of organic compounds.Meanwhile, increasing attention has been focused on twodimensional surface chirality. [1n,o, 2] Although chiral inorganic minerals have been considered to be an origin of chirality, achiral natural minerals with an enantiotopic surface have rarely been considered as an origin of chirality. A spectacular example was reported by Hazen et al. [3] They reported the enantiomer-selective adsorption of racemic amino acids on the enantiotopic faces of the achiral mineral calcite (CaCO 3 ) with moderate enantiomeric excess (Scheme 1 a). Certain metal surfaces, such as artificially cut Cu(643), become enantiotopic, and the enantiomer-selective decomposition of chiral compounds have been reported. [4] However, it has not yet been possible to control the enantioselective synthesis induced on the enantiotopic surface of achiral inorganic minerals to generate chiral molecules from achiral molecules.We have been studying asymmetric autocatalysis of pyrimidyl alkanol with amplification of chirality. [5][6][7][8] Various chiral factors, [9] including circularly polarized light, [10] isotope chirality, [11] and chiral inorganic crystals [12] trigger asymmetric autocatalysis. However, to the best of our knowledge, no definitive report has appeared on asymmetric synthesis using achiral inorganic crystals. [13] Gypsum is a common mineral that has been used in a wide range of applications, including materials for sculpture, plasterboard in buildings, and plaster casts for medical use. The crystal structure of gypsum is achiral, but its large grown face and its habit of cleavage make it enantiotopic. Although Cody and Cody have reported asymmetric crystal growth of the enantiotopic surface of gypsum in the presence of a chiral organic compound, [14] and Viedma, Cintas, et. al. have reported oriented aggregation growth of gypsum crystals, [15] no example has been reported of asymmetric synthesis on gypsum enantiotopic surfaces.Herein, we report enantioselective synthesis using the two-dimensional enantiotopic face of an achiral inorganic crystal (Scheme 1 b). The achiral inorganic mineral gypsum (calcium sulfate dihydrate, CaSO 4 ·2 H 2 O) triggers asymmetric autocatalysis on its enantiotopic face, thereby providing highly enantioenriched alkanol product with chirality corresponding to that of the enantiotopic face of the gypsum.Gypsum exhibits a p...

show abstract

Enantioselective CC Bond Formation as a Result of the Oriented Prochirality of an Achiral Aldehyde at the Single‐Crystal Face upon Treatment with a Dialkyl Zinc Vapor

Cited by 38 publications

References 52 publications

The Origins of Homochirality Examined by Using Asymmetric Autocatalysis

The Origins of Homochirality Examined by Using Asymmetric Autocatalysis

Achiral Organic, Inorganic, and Metal Crystals as Auxiliaries for Asymmetric Transformations

Achiral Inorganic Gypsum Acts as an Origin of Chirality through Its Enantiotopic Surface in Conjunction with Asymmetric Autocatalysis

Contact Info

Product

Resources

About