Computational studies of the aminolysis of oxoesters and thioesters in aqueous solution

Organic Letters

Volumn 2, Issue 26, 2000, Pages 4133-4136

  Yang, Wei ^a   Drueckhammer, Dale G ^a  

^a STONY BROOK UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001087039     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol006691l     Document Type: Article

References (24)

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15. All calculations except NBO calculations were carried out using the Gaussian 98 suite of programs: Gaussian 98, Revision A.7, Gaussian, Inc., Pittsburgh, PA, 1998.
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18. Calculations using the 6-31G** basis set, which allow the hydrogen atom to have characteristics of a p orbital predict a lower activation energy than that using 6-31+G* by 1.2-1.7 kcal/mol for oxoester aminolysis as well as for thioester aminolysis (see Figure 4). The small and fairly consistent differences between results using the 6-31G** and 6-31+G* basis sets show that these basis sets are sufficient to describe these systems and diffuse functions are not necessary. Energy levels are reported to a single decimal to reflect calculated energy differences, although 1-3 kcal/mol errors in absolute energies are likely.
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23. NBO Program Manual, Frank Weinhold, 1996.
24. C-X bond orders for the oxoester are 1.309 and 1.143 in the ground state and transition state, respectively, and for the thioester are 1.157 and 1.030.