Stereochemistry of Molecules in Crystals (part 1, 2)

Transcription

1 Stereochemistry of Molecules in Crystals (part 1, 2) umio Toda kayama University of Science, kayama, Japan key word: solid state, -guest complex part 1: statistic aspect part 2: dynamic aspect

2 : X a: X = b: X = (chiral) X 2 C C 2 rac, chiral 2 C R 2 2 C rac, chiral C C Br C rac, chiral -G complexation: /liq. G, /gas G, +G/solvent, +G grinding

3 1) acetylacetone-enol form part 1: statistic aspect (I) stereoisomers in inclusion crystals K, Bose 1998 Weber C 2 (R, R)-(-)- 2 2 C CrystEngComm

4 (R, R)-(-) C C ig. X-ray structures of inclusion complexes of acetylacetone.

5 2) acylic acid-monomeric s-trans form 2 C C 2 s-trans s-cis Chem. Comm. 1998, 2502.

6 2 C C 2 s-trans (a) (b) 1.20 Å 1.41 Å 1.38 Å 1.26 Å 46.5 º ig. 3 X-Ray analytical data: (a) stereoview of the complex and (b) bond lengths and dihedral angle for s-trans-acrylic acid in the complex.

7 2 C C 2 s-trans (a) ost (b) ost ost ost ost ost ig. 4 Schematic drawing: (a) a circle of three s-trans-acrylic acid molecules in the complex and (b) a circle of three s-cis-acrylic acid molecules, both involving disorder.

8 3) β-ionone hν s-cis retinal chromophore in rhodopsin s-trans s-trans ig. X-ray structure of the 2:1 complex.

9 2 C (R, R)-(-)- 2 C s-cis α-ionone ax-quasi-chair eq-quasi-chair Angew. Chem. Int. Ed. Engl. 1990, 662. Pure Appl. Chem. 1990, 417. Bio. rg. Chem. 1991, 157.

10 4) 1,2-dichloroethane Br (S)-(-)-2 yes no 1a trans θ = 36 º (M)-1b eclipsed Å (3.50 Å) C= ig. X-ray of a complex of (M)-1b. Chem. Comm. 1997, 1227.

11 θ = 5(4) º C 3

12 5) halocyclohexane - di-eq eq ax 2 C (R, R)-(-)- (-)- eq 2 C 90% ee Supramol. Chem. 2001, 175.

13 5) halocyclohexane eq X X eq ax a: X = ; b: X = Br rac - eq

14 eq- C streching ax- C streching rac - inclusion compound wavenumber (cm -1 ) ig. IR spectra with using ATR (attenuated total reflection).

15 ig. X-ray structure of the inclusion complex of eq-chlorocyclohexane.

16 rac - eq Br

17 rac - eq Br bromocyclohexane eq- C Br streching ax- C Br streching Br inclusion compound wavenumber (cm -1 ) ig. IR spectra with using ATR (attenuated total reflection). Chem. Comm. 2004, ig. X-ray structure.

18 5) halocyclohexane ax ax ig. X-ray structure of the complex.

19 ax ig. Packing diagram of ax-chlorocyclohexane complex which indicates the closest contacts.

20 ax ig. X-ray structure of normal and disordered ax-bromocyclohexane in the complex.

21 1,3-diaxial interaction (hydrogen bond?) Å Å Å Å disordered normal Å Å van der Walls radius;, 1.20 Å,, 1.75 Å A schematic structure of ax-chlorocyclohexane

22 Br ax Br 659 inclusion compound wavenumber (cm -1 ) 670 ig. IR spectra with using the ATR.

23 ax I (cps) 2 θ ax Br I (cps) 2 θ ig. X-ray powder diffraction pattern Chem. Comm. 2005, 3646.

24 6) cyclooctatrienone 11.9 kcal / mol hν hexane 21 days solution rac- 31% 2 hν 7 days solid (S, S)-(-)- (-)- 56% ee, not determined 7) cyclooctadienone cycloctadienone hν pentane rac- 1 h solution (S, S)-(-)- hν (-)- 48 h solid Tetrahedron Lett. 1988, 653, J. rg. Chem. 1990, % 78% ee 55%

25 8) enantiomerization tbu C brucine tbu + C (+)- (-)- tbu C dil. tbu (+)- C (+)- tbu C brucine 100% ee 100% yield Chem. Lett. 1983, 661.

26 (II) stereoisomers in own crystals 1) neighboring group effect R Br Br 2 R Br solid R Br Br R =,, Br solution R Acta Cryst. C , 620.

27 2) photochromism Zn-Zn 2 T- 2 chiral yellow dark hν yellow solution Chem. Comm. 2000, 873. triplet biradical D = G E = G g xx = purple red

28 3) oxoamide, generation of chirality (i) Pr i hν Pr i Pr i hν Pr i (+) in (+)-crystal in (-)-crystal (-) mirror 93% ee 93% ee Chem. Comm. 1987, 1413 J. Am. Chem. Soc. 1989, 697.

29 4) succinamide, generation of chilality (ii) Br 2 C Br 2 C C C 2 C C Br Br 2 C 2 C Br - 2 Br 2 C 2 C (+) (-) hν hν (+) (-) (+) 63% ee (-) Supramol. Chem. 1994, 87. Acta Cryst. B , 856.

30 2 C 2 C A chiral orange hexagonals mp 260 ºC B rac orange plates 302 ºC C rac yellow plates 297 ºC P2 1 Pbcn P2 1 /n