115119-00-1Relevant articles and documents
Formation by Mixing of Chiral Host-Achiral Guest Inclusion Complexes in which the Guest Molecules are Arranged in a Chiral Form. Production of Optically Active Photocyclisation Compounds by Irradiation of the Inclusion Complexes
Toda, Fumio,Miyamoto, Hisakazu,Kanemoto, Kazuyuki
, p. 1719 - 1720 (1995)
Mixing of powdered chiral hosts and achiral N,N-dialkylphenylglyoxylamide guest compounds gives inclusion complexes in which the latter molecules are arranged in a chiral form, although such complexes are not obtained by recrystallisation: the chirality of the guest compounds are frozen by photoreaction which gives optically active β-lactams and oxazolidinones.
Achiral molecules move and order themselves in a chiral form in host-guest inclusion crystals
Toda, Fumio,Miyamoto, Hisakazu
, p. 809 - 810 (1995)
When optically active host compound was mixed with achiral guest compound in the solid state, host-guest inclusion crystals were formed by molecular movement and the achiral molecules became arranged in a chiral form in the inclusion crystals.Mixing of powdered (+)-host crystals with powdered (-)-guest crystals which are formed by a chiral arrangement of achiral guest molecules gave inclusion crystals of (+)-host and the (+)-guest molecules newly produced through an inversion of the (-)-guest molecules during the complexation in the solid state.
Enantioselective cyanation/brook rearrangement/C-acylation reactions of acylsilanes catalyzed by chiral metal alkoxides
Nicewicz, David A.,Yates, Christopher M.,Johnson, Jeffrey S.
, p. 6548 - 6555 (2007/10/03)
New catalytic enantioselective cyanation/1,2-Brook rearrangement/C- acylation reactions of acylsilanes (4) with cyanoformate esters (7) are described. The products of the reaction are fully substituted malonic acid derivatives (8). Catalysts for this transformation were discovered via a directed candidate screen of 96 metal-ligand complexes. Optimization of a (salen)aluminum complex revealed significant remote electronic effects and concentration effects. The scope of the reaction was investigated by using a number of aryl acylsilanes and cyanoformate esters. Chemoselective reduction of the reaction products (8) afforded new enantioenriched α-hydroxy-α- aryl-β-amino acid derivatives (32-34) and β-lactams (35 and 36). This reaction provides a simple method for the construction of new nitrogen-containing enantioenriched chiral building blocks.
Catalytic asymmetric acylation of (silyloxy)nitrile anions
Nicewicz, David A.,Yates, Christopher M.,Johnson, Jeffrey S.
, p. 2652 - 2655 (2007/10/03)
An enantiopure (salen)aluminum alkoxide complex catalyzes the asymmetric coupling of acylsilanes and cyanoformate esters [Eq. (1), R = Bn, Et]. The reactions afford unsymmetrical, fully protected malonic acid derivatives that may be elaborated to nonnatural β-amino acid derivatives, and represent the first asymmetric catalytic reactions involving protected cyanohydrin anions.
Enantioselective photocyclization of amides to β-lactam derivatives in inclusion crystals with an optically active host
Toda, Fumio,Miyamoto, Hisakazu,Inoue, Mitsuhiro,Yasaka, Shunpei,Matijasic, Ivanka
, p. 2728 - 2732 (2007/10/03)
Irradiation of inclusion crystals of 2-(N-acyl-N-alkylamino)cyclohex-2- enones and N,N-dimethylphenylglyoxylamide with chiral host molecules gave the optically active N-alkyl-1-azaspiro[3,5]-nonane-2,5-diones and 3-hydroxy-1- methyl-3-phenylazetidin-2-one
Chiral Arrangement of N-Ethyl-N-isopropylphenylglyoxylamide Molecule in Its Own Crystal and in an Inclusion Crystal with a Host Compound and Their Photoreactions in the Solid State That Give Optically Active β-Lactam Derivatives. X-ray Analytical and CD Spectral Studies
Toda, Fumio,Miyamoto, Hisakazu,Koshima, Hideko,Urbanczyk-Lipkowska, Zofia
, p. 9261 - 9266 (2007/10/03)
N-Ethyl-N-isopropylphenylglyoxylamide (3c) forms chiral crystal in which its achiral molecules are arranged in a chiral form, and the chirality in the crystal was identified by measurement of the CD spectrum in Nujol mull. Generation of the chirality occurs by twisting of the CO-CO bond of 3c in the crystal. Photoirradiation of the chiral crystal of 3c in the solid state gave optically active β-lactam derivative (4c) of 80% ee. By X-ray analysis, absolute configurations of the chiral crystal and 4c were elucidated. The achiral molecules of 3c are also arranged in chiral forms in inclusion complexes with chiral hosts such as (R,R)-(-)-trans-2,3-bis(hydroxydiphenylmethyl)-1,4-dioxaspiro[4,4]nonane (5a), (R,R)-(-)-trans-2,3-bis(hydroxydiphenylmethyl)-1,4-dioxaspiro[5.4]-decane (5b), and their (S,S)-(+)-enantiomers, 6a and 6b, respectively. The crystal structure of a 1:1 inclusion complex of 3c with 5b (7b) was analyzed. Photoirradiation of 7b in the solid state gave (R)-(+)-4c of 85% ee. Photochemical conversions of some other derivatives of 3c to the corresponding β-lactams were also studied. Interestingly, however, irradiation of the 1:1 inclusion complex of N,N-dimethylglyoxylamide (3a) with 5a, which had been prepared by mixing both components in the absence of solvent, gave (R)-(+)-β-lactam (9a) of 45% ee, although the 1:1 complex that had been prepared by recrystallization of the components from toluene gave (S)-(-)-9a of 100% ee. Mixing of powdered chiral (-)-3c crystal with a 2:1 inclusion complex of 5b and MeOH gave a new 1:1 complex of 5b and chiral (+)-3c. The inversion of the chirality of 3c in the solid state was studied by continuous measurements of CD spectra in Nujol mulls.
Enantioselective photoreaction in inclusion crystal
Miyamoto, Hisakazu,Kikuchi, Siro,Oki, Yasuo,Inoue, Mitsuhiro,Kanemoto, Kazuyuki,Toda, Fumio
, p. 73 - 78 (2007/10/03)
Mixing of powdered chiral hosts and achiral guest compounds gives inclusion complexes in which the latter molecules are arranged in a chiral form. Freezing of the chirality of the guest compounds by photoirradiation in the solid state gives optically active photoreaction products.
Designs of host/guest molecular and crystal structures
Toda, Fumio
, p. 313 - 316 (2007/10/03)
When an optically active host compound was mixed with an achiral guest compound in the solid state, host-guest inclusion crystals were formed by molecular movement and the achiral molecules became arranged in a chiral form in the inclusion crystals.
Photocyclisation of Phenylglyoxylamides as Inclusion Complexes with an Optically Active Host Derived from Tartaric Acid: Delicate Dependence on the Substituent of the Host and Glyoxylamide
Toda, Fumio,Miyamoto, Hisakazu,Matsukawa, Rikiya
, p. 1461 - 1462 (2007/10/02)
Optically active β-lactams and/or oxazolidinones have been obtained selectively by photoirradiation of a 1:2 inclusion complex of phenylglyoxylamide with an optically active host derived from tartaric acid.Delicate selectivity which is dependent on substituents in the phenylglyoxylamide and the host is described.
ENANTIOCONTROLL OF PHOTOREACTIONS IN THE SOLID STATE
Toda Fumio
, p. 355 - 362 (2007/10/02)
Irradiation of crystalline complexes of prochiral guest compounds and optically active host compounds in the solid state gave optically active photoreaction products.For example, irradiation of the complexes of tropolone alkyl ether, nitrones, and oxoamid
