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Volumn 8, Issue 20, 2010, Pages 4589-4600

Quantum chemical dissection of the classic terpinyl/pinyl/bornyl/camphyl cation conundrum - The role of pyrophosphate in manipulating pathways to monoterpenes

Author keywords

[No Author keywords available]

Indexed keywords

COUNTERIONS; DIPHOSPHATES; ENERGY SURFACE; MONOTERPENES; QUANTUM CHEMICAL; QUANTUM CHEMICAL COMPUTATIONS; QUANTUM CHEMICAL STUDIES;

EID: 77957675477     PISSN: 14770520     EISSN: None     Source Type: Journal    
DOI: 10.1039/c0ob00167h     Document Type: Article
Times cited : (69)

References (96)
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    • See Supporting Information for details. We have exploited ammonia to assess structural distortions of carbocations previously 6 cit10 cit14 cit21 cit22 cit26 6,10,14,21,22,26
    • M. R. Siebert D. J. Tantillo J. Org. Chem. 2006 71 645 654
    • (2006) J. Org. Chem. , vol.71 , pp. 645-654
    • Siebert, M.R.1    Tantillo, D.J.2
  • 74
    • 0038341792 scopus 로고    scopus 로고
    • Pinene and camphene are also related to the sesquiterpenes bergamotene and santalene, respectively. See:
    • J. B. A. Hess Org. Lett. 2003 5 165 167
    • (2003) Org. Lett. , vol.5 , pp. 165-167
    • Hess, J.B.A.1
  • 79
    • 3242807342 scopus 로고    scopus 로고
    • We will describe calculations on these systems in due course In some cases, this may be a result of post-transition state bifurcations 13,23,43a,47
    • A. T. Kreipl W. A. Konig Phytochemistry 2004 65 2045 2049
    • (2004) Phytochemistry , vol.65 , pp. 2045-2049
    • Kreipl, A.T.1    Konig, W.A.2
  • 82
    • 77957661412 scopus 로고    scopus 로고
    • note
    • exo⋯N interaction is favorable for deprotonation to form α-pinene and the C10-H⋯N interaction is favorable for deprotonation to form β-pinene. Computations on these deprotonation reactions are described in the Supporting Information
  • 83
    • 77957670092 scopus 로고    scopus 로고
    • note
    • -1. See Supporting Information for details
  • 84
    • 77957681323 scopus 로고    scopus 로고
    • note
    • 18
  • 85
    • 77957659634 scopus 로고    scopus 로고
    • note
    • The B3LYP/6-31G(d) method was used for all of the pyrophosphate complexes due to their size. Test calculations using B3LYP/6-31+G(d,p) gave similar results. Details can be found in the Supporting Information. We also performed single point energy calculations using the BB1K, mPWB1K and MP2 methods on the B3LYP geometries shown in Fig. 7. The results led to similar conclusions as those based on the B3LYP/6-31G(d) calculations; see Supporting Information for these energies
  • 86
    • 77957663056 scopus 로고    scopus 로고
    • note
    • Our attempts included the use of constrained calculations and even larger models involving 3 magnesium ions; invariably, however, C-O bond formation occurred. We did find transition state structures for the direct interconversions of the pinyl cation and the camphyl cation in the presence of ammonia; see Supporting Information for details
  • 95
    • 0030845284 scopus 로고    scopus 로고
    • Formation of limonene was also examined; see Supporting Information for details
    • J. Bohlmann C. L. Steele R. Croteau J. Biol. Chem. 1997 272 21784 21792
    • (1997) J. Biol. Chem. , vol.272 , pp. 21784-21792
    • Bohlmann, J.1    Steele, C.L.2    Croteau, R.3


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.