(Salen)Mn-Catalyzed Epoxidation of Alkenes: A Two-Zone Process with Different Spin-State Channels as Suggested by DFT Study

Organic Letters

Volumn 6, Issue 1, 2004, Pages 59-62

  Abashkin, Yuri G ^a   Burt, Stanley K ^a  

^a SAIC FREDERICK INC   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKENE; MANGANESE;

ARTICLE; CALCULATION; CATALYSIS; CATALYST; EPOXIDATION;

ALKENES; CATALYSIS; EPOXY COMPOUNDS; ETHYLENEDIAMINES; MODELS, MOLECULAR; MOLECULAR STRUCTURE; ORGANOMETALLIC COMPOUNDS;

EID: 0742304183     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol036051t     Document Type: Article

References (27)

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24. (a) Becke-Perdue (BP) DFT approximation was used: Becke, A. D. Phys. Rev. 1988, A38, 3098. Perdew, J. P. Phys. Rev. 1986, B33, 8822. The Jaguar program with LACVP* basis (Jaguar 4.1; Schroedinger, Inc.: Portland, OR, 2000) was utilized for calculations that involved the complete model of the reaction: Jacobsen's catalyst plus the cis-Stilbene as the substrate. The Dgauss program (UniChem V4.0; Oxford Molecular: Oxford, UK) with DZVP basis was used to study the reaction profiles with the smaller model (see the text). (b) Using high level ab initio calculations (CCSD(T)), we recently showed (ref 4d) that the BP functional gives a realistic description of the relationship between the different spin channels involved in the studied reaction and is suitable for the reaction modeling. In contrast, using the B3LYP approach in this particular catalytic system case results in a distorted picture of the spin-state order. It was also pointed out that BP functional results may need some (likely, small) corrections since, on the product side of the reaction, the triplet and the quintet states are almost degenerated, although the quintet is known to be the resting state.
25. (a) Becke-Perdue (BP) DFT approximation was used: Becke, A. D. Phys. Rev. 1988, A38, 3098. Perdew, J. P. Phys. Rev. 1986, B33, 8822. The Jaguar program with LACVP* basis (Jaguar 4.1; Schroedinger, Inc.: Portland, OR, 2000) was utilized for calculations that involved the complete model of the reaction: Jacobsen's catalyst plus the cis-Stilbene as the substrate. The Dgauss program (UniChem V4.0; Oxford Molecular: Oxford, UK) with DZVP basis was used to study the reaction profiles with the smaller model (see the text). (b) Using high level ab initio calculations (CCSD(T)), we recently showed (ref 4d) that the BP functional gives a realistic description of the relationship between the different spin channels involved in the studied reaction and is suitable for the reaction modeling. In contrast, using the B3LYP approach in this particular catalytic system case results in a distorted picture of the spin-state order. It was also pointed out that BP functional results may need some (likely, small) corrections since, on the product side of the reaction, the triplet and the quintet states are almost degenerated, although the quintet is known to be the resting state.
26. Results will be published.
27. Both TR and FMR channels should be considered to get an accurate quantitative estimation of the reaction characteristics. The recent theoretical study (Jacobsen, H.; Cavallo, L. Chem. Eur. J. 2001, 7, 800-806), which managed to qualitatively explain the reaction enantiomeric excess using direct attack on the oxygen only, may indicate that both channels have the same stereoselectivity-determining step with branching after that step to reach the different catalytic zones. Our modeling does not contradict that picture, since TR and FMR reaction critical point structures can be easily qualitatively superimposed by rotation around the C1-O1 bond.