A Few Molecules Can Control the Enantiomeric Outcome. Evidence Supporting Absolute Asymmetric Synthesis Using the Soai Asymmetric Autocatalysis

Organic Letters

Volumn 5, Issue 23, 2003, Pages 4337-4339

  Singleton, Daniel A ^a   Vo, Loan K ^a  

^a TEXAS A AND M UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ARTICLE; CATALYSIS; CHEMICAL REACTION; ENANTIOMER; MOLECULAR DYNAMICS; SOAI ASYMMETRIC AUTOCATALYSIS; SYNTHESIS;

CATALYSIS; STEREOISOMERISM;

EID: 0345359342     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol035605p     Document Type: Article

References (39)

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31. (b) For closely related results, see: Sato, I.; Urabe, H.; Ishiguro, S.; Shibata, T.; Soai, K. Angew. Chem., Int. Ed. 2003, 42, 315 and particularly the unpublished results in footnote 12.
32. In our view, absolute asymmetric synthesis is not automatically precluded by the (likely unavoidable) presence of optically active impurities, so long as the optical activity arises as a first cause from random chance rather than the impurities or other asymmetric influences.
33. In the Soai work, the same reactions that afforded a stochastic mixture of enantiomers in ether/toluene led to nonrandom results in toluene alone.
34. In chronological order, the enantiomer obtained from ether reactions containing no additives has been: R,S,(R,S),(R,S),R,(R,S),(R,S),(S,S),(R,R),-(R, R),(R,S),(R,S),(R,R),(R,R), (R,R),(R,S),S,S,(S,S),(S,S),(R,S),(S,S),(R,S),-(S,S) ,(R,S),(S,S),(R,S),R, (R,R),(R,S). Sets of reactions in parentheses were carried out side-by-side using identical batches of starting materials.
35. A plausible alternative to random chance was that the product enantiomer could be controlled by the surface of the flask having a net optical activity. However, records kept of the enantiomer obtained from particular flasks show no sign of a "memory effect", that is, the same initial flask may afford either enantiomer in an apparently random pattern.
36. Sato, I.; Omiya, D.; Tsukiyama, K.; Ogi, Y. Soai, K. Tetrahedron: Asymmetry 2001, 12, 1965.
37. (a) It should be noted that the solution concentrations obtained by serial dilution are, at very low concentrations, theoretical, that is, not experimentally verified (or readily verifiable). It would be quite possible for adsorption of the solute to the surface of the flasks to result in concentrations that are much lower than theoretically expected. However, the results obtained are consistent with the theoretical concentrations.
38. -2 M solution of 4 in ether was prepared using 8.7 mg (0.05 mmol) of 4 in 5 mL of ether. Sequential dilutions were then prepared in new vials adding 100 μL of solution and 9.9 mL of purified ether by syringe. After each use, syringes were rinsed at least 10 times.
39. 3).