Mechanism of the conversion of inverted CB[6] to CB[6]

Journal of Organic Chemistry

Volumn 72, Issue 18, 2007, Pages 6840-6847

  Liu, Simin ^a   Kim, Kimoon ^b   Isaacs, Lyle ^a  

^a Bldg 142   (United States)

^b Pohang University of Science and Technology (POSTECH)   (South Korea)

Author keywords

[No Author keywords available]

Indexed keywords

AQUEOUS ACIDIC CONDITIONS; ISOTOPOMERS; RING CONTRACTION;

FORMALDEHYDE; MIXTURES; SYNTHESIS (CHEMICAL); THERMODYNAMICS;

STEREOCHEMISTRY;

ACETYLENEUREA; CUCURBIT[N]URIL DERIVATIVE; FORMALDEHYDE; GLYCOL; HYDROCHLORIC ACID; MACROCYCLIC COMPOUND; UNCLASSIFIED DRUG;

AQUEOUS SOLUTION; ARTICLE; CHEMICAL REACTION KINETICS; CHEMICAL STRUCTURE; DIASTEREOISOMER; GEOMETRY; HEATING; REACTION ANALYSIS; SYNTHESIS; THERMODYNAMICS;

EID: 34548763772     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo071034t     Document Type: Article

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60. To conclusively establish that the inverted glycoluril unit is extruded would require the availability of iCB[6] specifically isotopically labeled on the inverted glycoluril unit. Unfortunately, the statistical synthesis process makes such a compound inaccessible.
61. These experiments were performed with iCB[6] rather than iCB[7] because of its much greater abundance in the crude CB[n] forming reaction mixture and also its far greater ease of purification.
62. We have attempted to insert functionalized glycolurils or glycoluril cyclic ethers via a ring expansion process but were not able to isolate a single pure compound from these reactions. We believe that differential reactivity between 1 and functionalized glycolurils as well as stoichiometric imbalance between glycoluril and formaldehyde is responsible.
63. 2 symmetric and chiral. A related intermediate with Cs symmetry is also possible (Supporting Information) that leads to CB[6] in an analogous manner.
64. 12-iCB[6] is somewhat irregular, but reproducibly so, in that the peak intensities oscillate. We do not understand the cause of this effect.