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Volumn 14, Issue 8, 2008, Pages 2310-2320

(Me3Si)3SiH: Twenty years after its discovery as a radical-based reducing agent

Author keywords

Hydrosilylation; Radical reactions reduction; Silicon surfaces; Tris(trimethylsilyl)silane

Indexed keywords

HYDROSILYLATION; RADICAL REACTIONS REDUCTION; SILICON SURFACES; TRIS(TRIMETHYLSILYL)SILANE;

EID: 46049109074     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.200701415     Document Type: Article
Times cited : (138)

References (92)
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    • A number of reviews have described some aspects in comparison with other radical-based reducing agents, see: a P. A. Baguley, J. C. Walton, Angew. Chem. 1998, 110, 3272;
    • A number of reviews have described some aspects in comparison with other radical-based reducing agents, see: a) P. A. Baguley, J. C. Walton, Angew. Chem. 1998, 110, 3272;
  • 10
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    • Eds, P. Renaud, M. P. Sibi, Wiley-VCH, Weinheim
    • b) C. Chatgilialoglu, In Radical in Organic Synthesis, Vol. 1 (Eds.: P. Renaud, M. P. Sibi), Wiley-VCH, Weinheim, 2001, pp. 28-49;
    • (2001) Radical in Organic Synthesis , vol.1 , pp. 28-49
    • Chatgilialoglu, C.1
  • 13
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    • 3Si or the so called super silyl group as a bulky substituent or a protecting group are numerous: for recent applications,
    • 3Si or the so called "super silyl" group as a bulky substituent or a protecting group are numerous: for recent applications,
  • 19
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    • 3SiH has also been reported. see: T. Ruhland, J. Torang, H. Pedersen, J. C. Madsen, K. S. Bang, Synthesis 2005, 1635.
    • 3SiH has also been reported. see: T. Ruhland, J. Torang, H. Pedersen, J. C. Madsen, K. S. Bang, Synthesis 2005, 1635.
  • 34
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    • The recent debate on tris(trimetylsilyl)methane as reducing agent should be noted. It has clearly demonstrated (A. I. Longshaw, M. W. Carland, E. H. Krenske, M. L. Coote, M. S. Sherburn, Tetrahedron Lett. 2007, 48, 5585)
    • The recent debate on tris(trimetylsilyl)methane as reducing agent should be noted. It has clearly demonstrated (A. I. Longshaw, M. W. Carland, E. H. Krenske, M. L. Coote, M. S. Sherburn, Tetrahedron Lett. 2007, 48, 5585)
  • 35
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    • that this compound does not reduce organohalides under radical conditions as previously claimed (V. T. Perchyonok, Tetrahedron Lett. 2006, 47, 5163).
    • that this compound does not reduce organohalides under radical conditions as previously claimed (V. T. Perchyonok, Tetrahedron Lett. 2006, 47, 5163).
  • 37
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    • Earlier work from Roberts' laboratory showed that trialkylsilanes reduce alkyl halides to the corresponding hydrocarbons in the presence of alkanethiols (the so-called polarity-reversal catalysis in the radical-chain reduction). He demonstrated that the key step in these reductions is the hydrogen transfer from silane to the thiyl radical, which is strongly endothermic and reversible. For a review, see: B. P. Roberts, Chem. Soc. Rev. 1999, 28, 25;
    • a) Earlier work from Roberts' laboratory showed that trialkylsilanes reduce alkyl halides to the corresponding hydrocarbons in the presence of alkanethiols (the so-called polarity-reversal catalysis in the radical-chain reduction). He demonstrated that the key step in these reductions is the hydrogen transfer from silane to the thiyl radical, which is strongly endothermic and reversible. For a review, see: B. P. Roberts, Chem. Soc. Rev. 1999, 28, 25;
  • 38
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    • The same concept has been extended to catalysis of stannane-mediated radical chain reactions by benzeneselenol. For review see: D. Crich, D. Grant, V. Krishnamurthy, M. Patel. Acc. Chem. Res. 2007, 40, 453
    • b) The same concept has been extended to catalysis of stannane-mediated radical chain reactions by benzeneselenol. For review see: D. Crich, D. Grant, V. Krishnamurthy, M. Patel. Acc. Chem. Res. 2007, 40, 453.
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    • Eds, P. Renaud, M. P. Sibi, Wiley-VCH, Weinheim
    • b) Radicals in Organic Synthesis (Eds.: P. Renaud, M. P. Sibi), Wiley-VCH, Weinheim, 2001.
    • (2001) Radicals in Organic Synthesis
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    • nH, was carried out in refluxing toluene or 2,5-dimelhyl-THF by using AIBN as the radical initiator (see: Y.-L. Hsiao, R. M. Waymouth, J. Am. Chem. Soc. 1994, 116, 9779). Analogously, the introduction of sterically hindered amine groups through radical hydrosilylation of olefins or ketones allowed for the preparation of polysilanes as the polyolefin stabilizer
    • nH, was carried out in refluxing toluene or 2,5-dimelhyl-THF by using AIBN as the radical initiator (see: Y.-L. Hsiao, R. M. Waymouth, J. Am. Chem. Soc. 1994, 116, 9779). Analogously, the introduction of sterically hindered amine groups through radical hydrosilylation of olefins or ketones allowed for the preparation of polysilanes as the polyolefin stabilizer
  • 77
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    • For reviews, see: a
    • For reviews, see: a) J. M. Buriak, Chem. Rev. 2002, 102, 1271;
    • (2002) Chem. Rev , vol.102 , pp. 1271
    • Buriak, J.M.1
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    • [59b]
    • [59b]
  • 80
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    • 3SiH; for example, see: D. Wang, J. M. Buriak, Langmuir 2006, 22, 6214.
    • 3SiH; for example, see: D. Wang, J. M. Buriak, Langmuir 2006, 22, 6214.
  • 92
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    • 3SiH costs Euro 80.2 for 5 mL and Euro 244.5 for 25 mL (FLUKA 2007/2008 catalog) and due to its stability and possibility for titration, could also be bought (or sold) in larger quantities that are more economical. To date, the efficiency of the silane in terms of reactivity and diastereoselectivity has no comparison with the results obtained with other less expensive radical-based reagents. The invaluable absence of toxicity, as compared to the tin reagents. both for the operator and for the use of the products, (e.g. in biological assays), considerably elevates the benefit/cost ratio.
    • 3SiH costs Euro 80.2 for 5 mL and Euro 244.5 for 25 mL (FLUKA 2007/2008 catalog) and due to its stability and possibility for titration, could also be bought (or sold) in larger quantities that are more economical. To date, the efficiency of the silane in terms of reactivity and diastereoselectivity has no comparison with the results obtained with other less expensive radical-based reagents. The invaluable absence of toxicity, as compared to the tin reagents. both for the operator and for the use of the products, (e.g. in biological assays), considerably elevates the benefit/cost ratio.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.