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Volumn 14, Issue 20, 2008, Pages 6260-6268

Factors controlling the alkyne prins cyclization: The stability of dihydropyranyl cations

Author keywords

Alcohols; Cations; Cyclization; Rearrangement; Silanes

Indexed keywords

CYCLIZATION; IONS; POSITIVE IONS;

EID: 84963949845     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.200800281     Document Type: Article
Times cited : (34)

References (90)
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    • Direct Prins cyclization: a) M. J. Cloninger. L. E. Overman, J. Am. Chem. Soc. 1999, 121, 1092-1093;
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    • 3 was considered as just a Lewis acid.
    • 3 was considered as just a Lewis acid.
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    • A high-energy transition state B of the α-TMS allenyl cation 29 should exist; in this case, the ring-opening activation energy of the conversion of the trimelhylsilyl dihydropyranyl cation 28 into 29 is greater than from the conversion of 28 into cation 27. which requires only 0.2 kcal mol-1.
    • A high-energy transition state B of the α-TMS allenyl cation 29 should exist; in this case, the ring-opening activation energy of the conversion of the trimelhylsilyl dihydropyranyl cation 28 into 29 is greater than from the conversion of 28 into cation 27. which requires only 0.2 kcal mol-1.
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    • The energy comparison of several intermediates with a different number of atoms (e.g.. 25 and 28) is not possible by ab initio theoretical calculations; to allow this comparison we used the concept of an isodesmic reaction, a reaction (actual or hypothetical) in which the types of bonds made in forming the products are the same as those which are broken in the reactants (IUPAC definition. 1997).
    • The energy comparison of several intermediates with a different number of atoms (e.g.. 25 and 28) is not possible by ab initio theoretical calculations; to allow this comparison we used the concept of an isodesmic reaction, a reaction (actual or hypothetical) in which the types of bonds made in forming the products are the same as those which are broken in the reactants (IUPAC definition. 1997).
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    • For the reverse pathways from allenic alcohols to homopropargyl alcohols, see
    • For the reverse pathways from allenic alcohols to homopropargyl alcohols, see: K.-C. Lee, M.-J. Lin, T-P. Loh, Chem. Commun. 2004, 2456-2457.
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    • Lee, K.-C.1    Lin, M.-J.2    Loh, T.-P.3
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    • Prins cyclization can be considered to be the reverse of a Grob fragmentation; see
    • Prins cyclization can be considered to be the reverse of a Grob fragmentation; see R. W. Alder, J. N. Harvey, M. T. Oakley, J. Am. Chem. Soc. 2002, 124, 4960-4961.
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    • for a comprehensive review, see
    • d) for a comprehensive review, see: J. B. Lambert, Tetrahedron 1990, 46, 2677-2689;
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    • NMR characterization and X-ray structure of a β- disilacyclohenelidene-substituted vinyl cation has been reported; see: a T. Müller, R. Meyer, D. Lennartz, H.-U. Siehl, Angew. Chem. 2000, 112, 3203-3206;
    • NMR characterization and X-ray structure of a β- disilacyclohenelidene-substituted vinyl cation has been reported; see: a) T. Müller, R. Meyer, D. Lennartz, H.-U. Siehl, Angew. Chem. 2000, 112, 3203-3206;
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    • The numbering system is centered on the positively charged carbon atom
    • The numbering system is centered on the positively charged carbon atom.
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    • The triple bond has a symmetrical circular distribution of electronic density, and the ellipticity value is also zero as in the single bond case
    • The triple bond has a symmetrical circular distribution of electronic density, and the ellipticity value is also zero as in the single bond case.
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    • NBO 5.0, E. D. Glendenning, J. K. Badenhoop, A. E. Reed, J. E. Carpenter, J. A. Bohmann, C. M. Morales, F. Weinhold, Theoretical Chemistry Institute, University of Wisconsin, Madison. 2001: in the NBO analysis, the full-density matrix is partitioned into localized one- (core and lone pair) and two-center orbitais (the NBOs) that describe a Lewis-type structure.
    • NBO 5.0, E. D. Glendenning, J. K. Badenhoop, A. E. Reed, J. E. Carpenter, J. A. Bohmann, C. M. Morales, F. Weinhold, Theoretical Chemistry Institute, University of Wisconsin, Madison. 2001: in the NBO analysis, the full-density matrix is partitioned into localized one- (core and lone pair) and two-center orbitais (the NBOs) that describe a Lewis-type structure.
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    • In this hyperconjugative study, we have considered only the resonance structures with a contribution equal or greater than 10
    • In this hyperconjugative study, we have considered only the resonance structures with a contribution equal or greater than 10%.
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    • This interaction is similar to an alternative and widely accepted explanation of the anomeric effect, which is a stabilizing interaction between the unshared electron pair on the one heteroatom (the endocyclic one in a sugar ring) and the o* orbital for the axial (exocyclic) C-X bond: obviously, in our case there is no anomeric carbon atom
    • This interaction is similar to an alternative and widely accepted explanation of the anomeric effect, which is a stabilizing interaction between the unshared electron pair on the one heteroatom (the endocyclic one in a sugar ring) and the o* orbital for the axial (exocyclic) C-X bond: obviously, in our case there is no anomeric carbon atom.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.