Thionation of mesoionics with isothiocyanates: Evidence supporting a four-step domino process and ruling out a [2 + 2] mechanism

Journal of Organic Chemistry

Volumn 74, Issue 10, 2009, Pages 3698-3705

  Cantillo, David ^a   Ávalos, Martín ^a   Babiano, Reyes ^a   Cintas, Pedro ^a   Jiménez, José L ^a   Light, Mark E ^b   Palacios, Juan C ^a  

^a UNIVERSITY OF EXTREMADURA   (Spain)

^b UNIVERSITY OF SOUTHAMPTON   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

B3LYP/6-31G; BOND BREAKING REACTIONS; BOND FORMING; CHEMICAL EQUATIONS; CRYSTALLOGRAPHIC CHARACTERIZATION; DFT LEVELS; DOMINO PROCESS; DOUBLE BONDS; ELECTRONIC NATURES; EXCHANGE REACTION; HETEROCYCLES; ISOTHIOCYANATE; ISOTHIOCYANATES; SOLID-STATE STRUCTURES; THIOLATE; THIONATION;

CHEMICAL BONDS; O RINGS;

CHEMICAL REACTIONS;

AMPHOLYTE; HETEROCYCLIC COMPOUND; ISOTHIOCYANIC ACID DERIVATIVE; THIAZOLE DERIVATIVE;

ARTICLE; CHEMICAL BOND; CHEMICAL MODIFICATION; CRYSTALLOGRAPHY; DENSITY FUNCTIONAL THEORY; REACTION ANALYSIS; SOLID STATE; STRUCTURE ANALYSIS;

EID: 65949089380     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo900028c     Document Type: Article

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17. One of the reviewers has suggested to compute the corresponding transition structures for the rate-determining step of both domino and [2 + 2] reactions of compound 7 and PhNCS at a pure B3LYP/6-31G(d) level and using the IRC method. In doing so, we were able to obtain a significant energy difference between such TSs (21.8 kcal/mol), thereby fully corroborating the mecanistic proposal and supporting the ONIOM[B3LYP/6-31G(d):PM3] method as a reliable approach (see Supporting Information).