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Volumn 12, Issue 1, 2005, Pages 51-62

A formal total synthesis of eleutherobin using the ring-closing metathesis (RCM) reaction of a densely functionalized diene as the key step: Investigation of the unusual kinetically controlled RCM stereochemistry

Author keywords

Antitumor agents; Natural products; Ring closing metathesis; Stereocontrol; Total synthesis

Indexed keywords

ANTITUMOR AGENTS; NATURAL PRODUCTS; RING-CLOSING METATHESIS; STEREOCONTROL; TOTAL SYNTHESIS;

EID: 29344446565     PISSN: 09476539     EISSN: None     Source Type: Journal    
DOI: 10.1002/chem.200500749     Document Type: Article
Times cited : (49)

References (103)
  • 5
    • 4243476241 scopus 로고    scopus 로고
    • [Chem. Abstr. 1997, 126, P54863x].
    • (1997) Chem. Abstr. , vol.126
  • 7
    • 0344070371 scopus 로고    scopus 로고
    • [Chem. Abstr. 1996, 124, P194297z].
    • (1996) Chem. Abstr. , vol.124
  • 16
    • 0032486436 scopus 로고    scopus 로고
    • Angew. Chem. Int. Ed. 1998, 37, 1418-1421.
    • (1998) Angew. Chem. Int. Ed. , vol.37 , pp. 1418-1421
  • 45
  • 48
  • 49
    • 0034674322 scopus 로고    scopus 로고
    • Angew. Chem. Int. Ed. 2000, 39, 2073-2077;
    • (2000) Angew. Chem. Int. Ed. , vol.39 , pp. 2073-2077
  • 51
    • 0001399412 scopus 로고    scopus 로고
    • Angew. Chem. Int. Ed. 2000, 39, 3012-3043.
    • (2000) Angew. Chem. Int. Ed. , vol.39 , pp. 3012-3043
  • 61
    • 29344451476 scopus 로고    scopus 로고
    • note
    • H-5/H-6 = 16.5 Hz. The NOESY spectrum showed two positive cross peaks due to scalar coupling (E double bond), instead of two negative cross peaks due to NOE (Z double bond).
  • 62
    • 0034643997 scopus 로고    scopus 로고
    • The use of "second-generation" metathesis catalysts usually results in the selective formation of the thermodynamically favored stereoisomeric products in RCM reactions furnishing medium-sized rings, see: a) C. W. Lee, R. H. Grubbs, Org. Lett. 2000, 2, 2145-2147;
    • (2000) Org. Lett. , vol.2 , pp. 2145-2147
    • Lee, C.W.1    Grubbs, R.H.2
  • 67
    • 13244280043 scopus 로고    scopus 로고
    • f) J. Prunet, Angew. Chem. 2003, 115, 2932-2936;
    • (2003) Angew. Chem. , vol.115 , pp. 2932-2936
    • Prunet, J.1
  • 68
    • 0038373087 scopus 로고    scopus 로고
    • Angew. Chem. Int. Ed. 2003, 42, 2826-2830;
    • (2003) Angew. Chem. Int. Ed. , vol.42 , pp. 2826-2830
  • 71
    • 29344451018 scopus 로고    scopus 로고
    • note
    • 1), see the Experimental Section.
  • 74
    • 0023977798 scopus 로고
    • and references therein
    • (Z)-γ-(p-methoxyphenoxy)allyldiisopinocamphenylborane was prepared from (+)-α-pinene according to: H. C. Brown, P. K. Jadhav, K. S. Bhat. J. Am. Chem. Soc. 1988, 110, 1535-1538, and references therein.
    • (1988) J. Am. Chem. Soc. , vol.110 , pp. 1535-1538
    • Brown, H.C.1    Jadhav, P.K.2    Bhat, K.S.3
  • 75
    • 29344432891 scopus 로고    scopus 로고
    • note
    • H-5/H-6= 17.0 Hz is typical of an E double bond. The NOESY spectrum showed two positive cross peaks due to scalar coupling (E double bond), instead of two negative cross peaks due to NOE (Z double bond).
  • 76
    • 29344440828 scopus 로고    scopus 로고
    • note
    • b). The signal of the proton of the trisubstituted double bond (H-6, δ = 5.57 ppm) showed a coupling with the signal at δ= 4.72 ppm (H-7), which, in turn, coupled with the signal at δ= 4.25 ppm (H-8).
  • 81
    • 29344454720 scopus 로고    scopus 로고
    • note
    • The four low-quality torsional parameters are: two Lp-O3-C0*00 [for the Lp-O(sp3)-C(sp2)=O(sp2) torsion, ester group] and two H1-C2-C3-O3 [for the H-C(sp2)-C(sp3)-O(sp3) torsion, allylic ethers].
  • 82
    • 29344469127 scopus 로고    scopus 로고
    • note
    • The ten low-quality torsional parameters are: two Lp-O3-C0*00 [for the Lp-O(sp3)-C(sp2)=O(sp2) torsion, ester group], two H1-C2-C3-O3 [for the H-C(sp2)-C(sp3)-O(sp3) torsion, allylic ethers], two 00-C3-O3-00 [for the C(sp2)-C(sp3)-O(sp3)-C(sp2) torsion, allylic phenyl ethers], four Lp-O3-C0*00 [for the Lp-O(sp3)-C(sp2)= C(sp2) torsion, phenyl ethers].
  • 83
    • 29344474511 scopus 로고    scopus 로고
    • note
    • The six low-quality torsional parameters are: two Lp-O3-C0*00 [for the Lp-O(sp3)-C(sp2)=O(sp2) torsion, ester group], one 00*C2= C2*00 [for the (O=)C-CH=CH-C(=O) torsion, enedione], two 00-C2-C3-00 [for the O(sp3)-C(sp3)-C(sp2)-C(sp2) torsion], one C0-C3-O3-C2 [for the (O=)C-C(sp3)-O(sp3)-C(=O) torsion].
  • 85
    • 0000338310 scopus 로고    scopus 로고
    • For an interesting case of kinetic control in a second-generation Grubbs catalyzed cross-metathesis reaction, see: F. C. Engelhardt, M. J. Schmitt, R. E. Taylor, Org. Lett. 2001, 3, 2209-2212.
    • (2001) Org. Lett. , vol.3 , pp. 2209-2212
    • Engelhardt, F.C.1    Schmitt, M.J.2    Taylor, R.E.3
  • 88
    • 29344465801 scopus 로고    scopus 로고
    • note
    • The Ru atom was substituted with a carbon atom. The "frozen" core structure (corresponding to the original ruthenacyclobutane fragment including the substituents at ruthenium) maintained its initial geometry, while the rest of the structure was smoothly minimized. After the conformational search and the minimization, the Ru atom was reinstalled, and the structures were optimized with the DFT calculations.
  • 91
    • 0345491105 scopus 로고
    • Becke's three-parameter hybrid method using the LYP (C. Lee, W. Yang, R. G. Parr, Phys. Rev. B 1988, 37, 785-789)
    • (1988) Phys. Rev. B , vol.37 , pp. 785-789
    • Lee, C.1    Yang, W.2    Parr, R.G.3
  • 92
    • 0000189651 scopus 로고
    • correlation functional: A. D. Becke, J. Chem. Phys. 1993, 98, 5648-5652.
    • (1993) J. Chem. Phys. , vol.98 , pp. 5648-5652
    • Becke, A.D.1
  • 93
    • 0003568278 scopus 로고
    • (Ed.: H. F. Schaeffer III), Plenum, New York
    • The LANL2DZ basis set consists of the valence double-zeta D95 V basis set for first-row atoms (T. H. Dunning, Jr., P. J. Hay in Modern Theoretical Chemistry (Ed.: H. F. Schaeffer III), Plenum, New York. 1976, pp. 1-28)
    • (1976) Modern Theoretical Chemistry , pp. 1-28
    • Dunning Jr., T.H.1    Hay, P.J.2
  • 94
    • 33745770836 scopus 로고
    • and the Los Alamos effective core potential (P. J. Hay, W. R. Wadt, J. Chem. Phys. 1985, 82, 270-283) for Cl and Ru.
    • (1985) J. Chem. Phys. , vol.82 , pp. 270-283
    • Hay, P.J.1    Wadt, W.R.2


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.