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Volumn 44, Issue 23, 2005, Pages 3548-3552

Dynamic effects on [3,3] and [1,3] shifts of 6-methylenebicyclo[3.2.0]hept- 2-ene

Author keywords

Ab initio calculations; Density functional calculations; Diastereoselectivity; Reaction mechanisms; Sigmatropic rearrangement

Indexed keywords

BIFURCATION (MATHEMATICS); BONDING; DEUTERIUM; DYNAMICS;

EID: 20544464487     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200500027     Document Type: Article
Times cited : (33)

References (26)
  • 16
    • 20544448658 scopus 로고
    • PhD Dissertation, Ruhr University, Bochum (Germany)
    • a) P.-J. Rissing, PhD Dissertation, Ruhr University, Bochum (Germany), 1978;
    • (1978)
    • Rissing, P.-J.1
  • 17
    • 20544456804 scopus 로고    scopus 로고
    • PhD Dissertation, Ruhr University, Bochum (Germany)
    • b) D. Baumann, PhD Dissertation, Ruhr University, Bochum (Germany), 2001.
    • (2001)
    • Baumann, D.1
  • 19
    • 20544464648 scopus 로고    scopus 로고
    • note
    • It is immediately evident that TS-23n forms a bond from C3 to the proximal allyl terminus. Although it appears feasible that TS-23x might involve rotation of the distal allyl carbon past C4 and into bonding distance with C3, IRC calculations show that this is not the case: the bond is formed to the proximal carbon in TS-23x as well as TS-23n.
  • 20
    • 20544463652 scopus 로고    scopus 로고
    • note
    • 21 is the same for all intermediates 2, and therefore may be ignored in the computation of label distribution in product 3.
  • 21
    • 20544434371 scopus 로고    scopus 로고
    • note
    • A transition state for a concerted [3s,3s] reaction, as well as one for a concerted [1i,3s] process, can be located with RB3LYP/6-31G(d) (Supporting Information), but these saddle points are only artifacts of the restricted formalism, and they disappear at the UB3 LYP level.
  • 22
    • 20544456350 scopus 로고    scopus 로고
    • note
    • A CASPT2 single-point energy calculation was performed on each of the UB3 LYP constrained-optimized structures used to construct the UB3 LYP surface.
  • 23
    • 0037055058 scopus 로고    scopus 로고
    • A PES involving a post-TS bifurcation between a Cope pathway and formation of an allylic-stabilized diradical intermediate has been discussed in the case of an acyclic allenic triene: S. L. Debbert, B. K. Carpenter, D. A. Hrovat, W. T. Borden, J. Am. Chem. Soc. 2002, 124, 7896.
    • (2002) J. Am. Chem. Soc. , vol.124 , pp. 7896
    • Debbert, S.L.1    Carpenter, B.K.2    Hrovat, D.A.3    Borden, W.T.4


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.