메뉴 건너뛰기




Volumn 75, Issue 2, 2010, Pages 455-463

Origin of stereocontrol in the construction of the 12-oxatricyclo[6.3.1. 02,7]dodecane ring system by Prins-pinacol reactions

Author keywords

[No Author keywords available]

Indexed keywords

CHEMICAL EQUATIONS; CYCLIZATIONS; DODECANE; MOLECULAR REARRANGEMENT; OXOCARBENIUM; PINACOLS; PRINS CYCLIZATION; RING SYSTEMS; STEREOCONTROL; STERIC EFFECT;

EID: 75349083884     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo9024144     Document Type: Article
Times cited : (20)

References (49)
  • 5
    • 34250810082 scopus 로고    scopus 로고
    • Metal Catalyzed Cascade Reactions
    • Müller, T. J. J, Ed, Springer-Verlag: Berlin, Germany
    • (e) Müller, T. J. J., Ed. Metal Catalyzed Cascade Reactions. In Topics in Organometallic Chemistry; Springer-Verlag: Berlin, Germany, 2006; Vol 19.
    • (2006) Topics in Organometallic Chemistry , vol.19
  • 15
    • 0141678121 scopus 로고    scopus 로고
    • For recent reviews, see: a
    • For recent reviews, see: (a) Overman, L. E.; Pennington, L. D. J. Org. Chem. 2003, 68, 7143-7157.
    • (2003) J. Org. Chem , vol.68 , pp. 7143-7157
    • Overman, L.E.1    Pennington, L.D.2
  • 19
    • 0001290261 scopus 로고
    • For reviews, see: a, Trost, B. M, Fleming, I, Heathcock, C. H, Eds, Pergamon Press: NewYork
    • For reviews, see: (a) Snider, B. B. In The Prins Reaction and Carbonyl Ene Reactions; Trost, B. M., Fleming, I., Heathcock, C. H., Eds.; Pergamon Press: NewYork, 1991;Vol. 2, pp 527-561.
    • (1991) The Prins Reaction and Carbonyl Ene Reactions , vol.2 , pp. 527-561
    • Snider, B.B.1
  • 23
    • 32144450591 scopus 로고    scopus 로고
    • For a quite different approach to the construction of the trans variant of this oxatricyclic ring system, see: Molander, G. A, Czakó, B, St. Jean, D. J, Jr. J. Org. Chem. 2006, 71, 1172-1180
    • For a quite different approach to the construction of the trans variant of this oxatricyclic ring system, see: Molander, G. A.; Czakó, B.; St. Jean, D. J., Jr. J. Org. Chem. 2006, 71, 1172-1180.
  • 24
    • 75349095286 scopus 로고    scopus 로고
    • Ph.D. Dissertation, University of California, Irvine
    • Velthuisen, E. J. Ph.D. Dissertation, University of California, Irvine, 2005.
    • (2005)
    • Velthuisen, E.J.1
  • 25
    • 75349098679 scopus 로고    scopus 로고
    • The preparation of cyclohexenyl iodides 10a-e is described in the Supporting Information.
    • The preparation of cyclohexenyl iodides 10a-e is described in the Supporting Information.
  • 26
    • 33746485436 scopus 로고
    • The revised Pauling electronegativity of sulfur is 2.58 (similar to carbon, 2.55), whereas for oxygen it is 3.44: Allred, A. L
    • The revised Pauling electronegativity of sulfur is 2.58 (similar to carbon, 2.55), whereas for oxygen it is 3.44: Allred, A. L. J. Inorg. Nucl. Chem. 1961, 17, 215-221.
    • (1961) J. Inorg. Nucl. Chem , vol.17 , pp. 215-221
  • 29
    • 75349098072 scopus 로고    scopus 로고
    • Crystallographic data for this compound were deposited at the Cambridge Crystallographic Data Centre: CCDC 753122. An ORTEP diagram of compound 18b may be found in the Supporting Information. As is evident in this diagram, the aldehyde hydrogen atom projects close to the oxo bridge and directly into the cavity of the molecule
    • Crystallographic data for this compound were deposited at the Cambridge Crystallographic Data Centre: CCDC 753122. An ORTEP diagram of compound 18b may be found in the Supporting Information. As is evident in this diagram, the aldehyde hydrogen atom projects close to the oxo bridge and directly into the cavity of the molecule.
  • 30
    • 75349094784 scopus 로고    scopus 로고
    • An alternate explanation for the stereoselection observed in Prins-pinacol reactions that has not yet been probed thoroughly is the possibility that the cyclization and rearrangement steps occur with some degree of concert. Computational studies to evaluate this possibility are underway
    • An alternate explanation for the stereoselection observed in Prins-pinacol reactions that has not yet been probed thoroughly is the possibility that the cyclization and rearrangement steps occur with some degree of concert. Computational studies to evaluate this possibility are underway.
  • 31
    • 75349111609 scopus 로고    scopus 로고
    • In the absence of stereoelectronic constraints, pinacol rearrangements have low activation barriers, see: (a) Bartok, M, Molnar, A. In Chemistry of Ethers, Crown Ethers, Hydroxyl Compounds and Their Sulfur Analogues; Patai, S, Ed, Wiley: New York, 1980; Part 2, pp 722-732
    • In the absence of stereoelectronic constraints, pinacol rearrangements have low activation barriers, see: (a) Bartok, M.; Molnar, A. In Chemistry of Ethers, Crown Ethers, Hydroxyl Compounds and Their Sulfur Analogues; Patai, S., Ed.; Wiley: New York, 1980; Part 2, pp 722-732.
  • 32
    • 0000382638 scopus 로고
    • Trost, B. M, Fleming, I, Eds, Pergamon Press: Oxford, UK
    • (b) Rickborn, B. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: Oxford, UK, 1991; Vol. 3, pp 721-732.
    • (1991) Comprehensive Organic Synthesis , vol.3 , pp. 721-732
    • Rickborn, B.1
  • 33
    • 0030877492 scopus 로고    scopus 로고
    • For a particularly revealing example, see
    • For a particularly revealing example, see: Minor, K. P.; Overman, L. E. Tetrahedron 1997, 53, 8927-8940.
    • (1997) Tetrahedron , vol.53 , pp. 8927-8940
    • Minor, K.P.1    Overman, L.E.2
  • 34
    • 75349114077 scopus 로고    scopus 로고
    • The three-dimensional models shown in Schemes 3 and 4 were generated by the analysis of 15-20 low-energy conformers using MMFF conformational searches (Spartan '08 for Macintosh; Wavefunction, Inc.; Irvine, CA, 2008) on cations derived from Prins cyclization of dimethyl substrates 14e and 15e, followed by DFT geometry optimization at the B3LYP/6-31G* level. Minima containing strong deformation of the carbocationic center toward a sulfur atom of the dithiane substituent or ones that could not be formed directly by the Prins reaction were disregarded.
    • The three-dimensional models shown in Schemes 3 and 4 were generated by the analysis of 15-20 low-energy conformers using MMFF conformational searches (Spartan '08 for Macintosh; Wavefunction, Inc.; Irvine, CA, 2008) on cations derived from Prins cyclization of dimethyl substrates 14e and 15e, followed by DFT geometry optimization at the B3LYP/6-31G* level. Minima containing strong deformation of the carbocationic center toward a sulfur atom of the dithiane substituent or ones that could not be formed directly by the Prins reaction were disregarded.
  • 35
    • 53649101167 scopus 로고    scopus 로고
    • For an incisive analysis of the structure of oxocarbenium ions bearing proximal heteroatoms, and evidence against bridging from an adjacent sulfur atom to form a stable episulfonium ion intermediate, see
    • For an incisive analysis of the structure of oxocarbenium ions bearing proximal heteroatoms, and evidence against bridging from an adjacent sulfur atom to form a stable episulfonium ion intermediate, see: Beaver, M. G.; Billings, S. B.; Woerpel, K. A. Eur. J. Org. Chem. 2008, 771-781.
    • (2008) Eur. J. Org. Chem , pp. 771-781
    • Beaver, M.G.1    Billings, S.B.2    Woerpel, K.A.3
  • 39
    • 75349102414 scopus 로고    scopus 로고
    • A similar chair preference was seen in the Prins-pinacol reaction of the configurationally analogous, structurally less elaborate, precursor (compound 16 in our earlier study).8
    • 8
  • 40
    • 75349097428 scopus 로고    scopus 로고
    • 22 (see the Supporting Information for details). (Chemical Equation Presented)
    • 22 (see the Supporting Information for details). (Chemical Equation Presented)
  • 41
    • 75349113075 scopus 로고    scopus 로고
    • For a recent computational study and detailed discussion of the donor ability of C-H bonds to adjacent vacant p-orbitals, see ref 21b
    • For a recent computational study and detailed discussion of the donor ability of C-H bonds to adjacent vacant p-orbitals, see ref 21b.
  • 43
    • 0037099465 scopus 로고    scopus 로고
    • For reviews of 1,2-sulfur migrations, see: a
    • For reviews of 1,2-sulfur migrations, see: (a) Fox, D. J.; House, D.; Warren, S. Angew. Chem., Int. Ed. 2002, 41, 2462-2482.
    • (2002) Angew. Chem., Int. Ed , vol.41 , pp. 2462-2482
    • Fox, D.J.1    House, D.2    Warren, S.3
  • 47
    • 75349092613 scopus 로고    scopus 로고
    • The formation of products 18 is the first example of a thio-Prins-pinacol sequence in which the initial thio-Prins cyclization generates a seven-membered ring.
    • The formation of products 18 is the first example of a thio-Prins-pinacol sequence in which the initial thio-Prins cyclization generates a seven-membered ring.
  • 48
    • 75349103753 scopus 로고    scopus 로고
    • Representative experimental procedures for preparing a cyclization substrate and its rearrangement upon reaction with SnCl4. General experimental details, experimental procedures, and characterization for other new compounds can be found in the Supporting Information
    • 4. General experimental details, experimental procedures, and characterization for other new compounds can be found in the Supporting Information.
  • 49
    • 75349103919 scopus 로고    scopus 로고
    • 18b is highly crystalline, and after crystallization is difficult to redissolve in standard chromatography solvents
    • Byproduct 18b is highly crystalline, and after crystallization is difficult to redissolve in standard chromatography solvents. As a result, some product was lost during purification.
    • As a result, some product was lost during purification
    • Byproduct1


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.