Stereoselective recognition of vicinal diamines with a Zn(II) complex

Journal of Organic Chemistry

Volumn 71, Issue 23, 2006, Pages 8966-8968

  Kim, Woosung ^a,b   So, Soon Mog ^a   Chagal, Leonid ^b   Lough, Alan J ^b   Kim, B Moon ^a   Chin, Jik ^b  

^a Seoul National University   (South Korea)

^b UNIVERSITY OF TORONTO   (Canada)

Author keywords

[No Author keywords available]

Indexed keywords

CRYSTALLOGRAPHY; MOLECULAR STRUCTURE; NUCLEAR MAGNETIC RESONANCE; REACTION KINETICS; STEREOCHEMISTRY; ZINC;

1,2-DIAMINOCYCLOHEXANE (DACH); RACEMIC MIXTURES; STERIC EFFECTS; VICINAL DIAMINES;

AMINES;

DIAMINE; METAL COMPLEX; ZINC COMPLEX;

ARTICLE; CHEMICAL REACTION; CHEMICAL STRUCTURE; COMPLEX FORMATION; DIASTEREOISOMER; PROTON NUCLEAR MAGNETIC RESONANCE; STEREOCHEMISTRY;

EID: 33750870091     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo0616815     Document Type: Article

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17. A small amount of the homochiral complex is visible in Figure 2b. This is because commercial (S,S)-dpen is contaminated with its enantiomer and the homochiral complex is more stable than the heterochiral complex. Although commercial (R,R)-dpen is also contaminated with its enantiomer, the heterochiral complex is not visible in Figure 2a because it is less stable than the homochiral complex. Figure 2c can also be generated with enantiopure host and racemic guest.
18. Comparable selectivity is found when dmso is used as solvent instead of methanol.
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22. DFT computation was performed using Spartan '04 Windows; Wavefunction, Inc.: Irving, CA, 2004.
23. Although the computations are used here for qualitative trends, the observed stereoselectivity (1.0 kcal/mol) for formation of the ternary complex in Figure 1 is in good agreement with the computed stereoselectivity (1.2 kcal/mol). Molecular mechanics and PM3 semiempirical computations also show the same trend (Supporting Information).
24. 1H NMR increases dramatically from the lowering of both levels of stereoselectivity.