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Volumn 10, Issue 4, 2008, Pages 685-687

One-pot synthesis of meso-formylporphyrins by SNAr reaction of 5, 15-disubstituted porphyrins with (2-pyridyldimethylsilyl)methyllithium

Author keywords

[No Author keywords available]

Indexed keywords

LITHIUM; ORGANOMETALLIC COMPOUND; PORPHYRIN; SILICON;

EID: 39749122648     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol703107t     Document Type: Article
Times cited : (23)

References (35)
  • 1
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    • Kadish, K. M, Smith, K. M, Guilard, R, Eds, Academic Press: San Diego, Vols
    • The Porphyrin Handbook; Kadish, K. M., Smith, K. M., Guilard, R., Eds.; Academic Press: San Diego, 1999-2003; Vols. 1-20.
    • (1999) The Porphyrin Handbook , vol.1-20
  • 2
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    • We have developed porphyrin-based Lewis acid catalysts that can promote regio- and stereoselective isomerization of epoxides to carbonyl compounds and Claisen rearrangement of allylvinyl ethers; see: (a) Suda, K, Baba, K, Nakajima, S, Takanami, T. Chem. Commun. 2002, 2570-2571
    • We have developed porphyrin-based Lewis acid catalysts that can promote regio- and stereoselective isomerization of epoxides to carbonyl compounds and Claisen rearrangement of allylvinyl ethers; see: (a) Suda, K.; Baba, K.; Nakajima, S.; Takanami, T. Chem. Commun. 2002, 2570-2571.
  • 6
    • 85006518549 scopus 로고
    • For some examples of leading works on functionalization reactions of porphyrins, see: a
    • For some examples of leading works on functionalization reactions of porphyrins, see: (a) DiMagno, S. G.; Lin, V. S.-Y.; Therien, M. J. J. Am. Chem. Soc. 1993, 115, 2513-2515.
    • (1993) J. Am. Chem. Soc , vol.115 , pp. 2513-2515
    • DiMagno, S.G.1    Lin, V.S.-Y.2    Therien, M.J.3
  • 10
    • 26644434833 scopus 로고    scopus 로고
    • have developed a unique, yet useful, method for the preparation of meso-substituted porphyrins utilizing an SNAr reaction with organolithium reagents: (a) Senge, M. O
    • Senge et al. have developed a unique, yet useful, method for the preparation of meso-substituted porphyrins utilizing an SNAr reaction with organolithium reagents: (a) Senge, M. O. Acc. Chem. Res. 2005, 38, 733-743.
    • (2005) Acc. Chem. Res , vol.38 , pp. 733-743
    • Senge1
  • 13
    • 0042381716 scopus 로고    scopus 로고
    • We have reported metal-catalyzed amination and cyanation of porphyrins: (a) Takanami, T, Hayashi, M, Hino, F, Suda, K. Tetrahedron Lett. 2003, 44, 7353-7357
    • We have reported metal-catalyzed amination and cyanation of porphyrins: (a) Takanami, T.; Hayashi, M.; Hino, F.; Suda, K. Tetrahedron Lett. 2003, 44, 7353-7357.
  • 21
    • 39749146293 scopus 로고    scopus 로고
    • A multi-step total synthesis of free base meso-formylporphyrins has been reported by Lindsey et al, see ref 6a
    • A multi-step total synthesis of free base meso-formylporphyrins has been reported by Lindsey et al.; see ref 6a.
  • 22
    • 0001122697 scopus 로고
    • For reviews: a, Trost, B. M, Fleming, I, Eds, Pergamon: Oxford
    • For reviews: (a) Colvin, E. W. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: Oxford, 1991; Vol. 7, pp 641-651.
    • (1991) Comprehensive Organic Synthesis , vol.7 , pp. 641-651
    • Colvin, E.W.1
  • 27
    • 39749155617 scopus 로고    scopus 로고
    • Although we have failed in isolating meso-hydroxymethylporphyrin 5a, a key synthetic intermediate in this formylation, TLC analysis snowed that the hydroxymethyl derivative 5a transiently appears during the course of the reaction: the Rf value (0.21, THF/hexane, 1:2) of the hydroxymethyl derivative 5a proved to be identical to that of an authentic sample independently prepared by the reduction of the meso-formylporphyrin 2a with NaBH4 in THF/MeOH (3:1) at room temperature
    • 4 in THF/MeOH (3:1) at room temperature.
  • 28
    • 39749130829 scopus 로고    scopus 로고
    • Although details of the oxidation processes of silylmethylporphyrin 4 and hydroxymethylporphyrin 5 are not yet clear, we tentatively assume the mechanism depicted in the following scheme, where each oxidation reaction is initiated by a single-electron transfer from the respective compounds, 4 and 5 (see refs 13 and 14, to DDQ, a well-known electron acceptor see refs 15 and 16, Further experiments are currently underway to elucidate the mechanism in detail
    • Although details of the oxidation processes of silylmethylporphyrin 4 and hydroxymethylporphyrin 5 are not yet clear, we tentatively assume the mechanism depicted in the following scheme, where each oxidation reaction is initiated by a single-electron transfer from the respective compounds, 4 and 5 (see refs 13 and 14), to DDQ, a well-known electron acceptor (see refs 15 and 16). Further experiments are currently underway to elucidate the mechanism in detail.
  • 29
    • 33646462101 scopus 로고    scopus 로고
    • For reviews on electron-transfer oxidation of organosilicon compounds, see: a
    • For reviews on electron-transfer oxidation of organosilicon compounds, see: (a) Yoshida, J.; Nishiwaki, K. J. Chem. Soc., Dalton Trans 1998, 2589-2596.
    • (1998) J. Chem. Soc., Dalton Trans , pp. 2589-2596
    • Yoshida, J.1    Nishiwaki, K.2
  • 31
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    • For reviews on electron-transfer oxidation of alcohols, see: a, Springer-Verlag: Berlin
    • For reviews on electron-transfer oxidation of alcohols, see: (a) Shono, T. Electroorganic Chemistry as a New Tool in Organic Synthesis; Springer-Verlag: Berlin, 1984; pp 29-38.
    • (1984) Electroorganic Chemistry as a New Tool in Organic Synthesis , pp. 29-38
    • Shono, T.1
  • 34
    • 3943069018 scopus 로고    scopus 로고
    • and references cited therein. Several groups have reported that DDQ can oxidize aryl methanols to aromatic aldehydes; see
    • Several groups have reported that DDQ can oxidize aryl methanols to aromatic aldehydes; see: Branytska, O.; Neumann, R. Synlett 2004, 1575-1576 and references cited therein.
    • (2004) Synlett , pp. 1575-1576
    • Branytska, O.1    Neumann, R.2
  • 35
    • 39749193773 scopus 로고    scopus 로고
    • 2/MeOH (3:1) at room temperature gave the corresponding Zn(II) complexes in quantitative yields.
    • 2/MeOH (3:1) at room temperature gave the corresponding Zn(II) complexes in quantitative yields.


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