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Volumn 75, Issue 15, 2010, Pages 5083-5091

Phosphine-catalyzed reductions of alkyl silyl peroxides by titanium hydride reducing agents: Development of the method and mechanistic investigations

Author keywords

[No Author keywords available]

Indexed keywords

CATALYTIC AMOUNTS; CHEMOSELECTIVE REDUCTION; CROSSOVER EXPERIMENTS; HYDROPEROXIDES; OXYGEN ATOM; PHOSPHINE OXIDE; SILICON ATOMS; SILYL GROUP; SUBSEQUENT REDUCTION; TITANIUM ALKOXIDES; TITANIUM HYDRIDE;

EID: 77955157299     PISSN: 00223263     EISSN: 15206904     Source Type: Journal    
DOI: 10.1021/jo1008367     Document Type: Article
Times cited : (68)

References (123)
  • 12
    • 77955137024 scopus 로고    scopus 로고
    • references cited within
    • Allen, D. W. Organophosphorus Chem. 2008, 37, 13-53 and references cited within.
    • (2008) Organophosphorus Chem. , vol.37 , pp. 13-53
    • Allen, D.W.1
  • 13
    • 77955134324 scopus 로고
    • For examples of reductions of peroxides by metal hydrides, see
    • For examples of reductions of peroxides by metal hydrides, see: Matic, M.; Sutton, D. A. J. Chem. Soc. 1952, 2679-2682
    • (1952) J. Chem. Soc. , pp. 2679-2682
    • Matic, M.1    Sutton, D.A.2
  • 17
    • 0000492816 scopus 로고
    • For an example of reductions of hydroperoxides by silanes and stannanes, see
    • For an example of reductions of hydroperoxides by silanes and stannanes, see: Nakamura, E.; Sato, K.-i.; Imanishi, Y. Synlett 1995, 525-526
    • (1995) Synlett , pp. 525-526
    • Nakamura, E.1    Sato, K.-I.2    Imanishi, Y.3
  • 18
    • 33845281614 scopus 로고
    • The formation of a phosphine oxide from a phosphine and oxygen is exothermic, so a phosphine oxide would not be expected to be a strong oxygen atom donor. Conversely, the formation of peroxide from an alcohol and oxygen is endothermic, so a peroxide would be more likely to serve as an oxygen transfer agent. For examples and a discussion, see
    • The formation of a phosphine oxide from a phosphine and oxygen is exothermic, so a phosphine oxide would not be expected to be a strong oxygen atom donor. Conversely, the formation of peroxide from an alcohol and oxygen is endothermic, so a peroxide would be more likely to serve as an oxygen transfer agent. For examples and a discussion, see: Holm, R. H. Chem. Rev. 1987, 87, 1401-1449
    • (1987) Chem. Rev. , vol.87 , pp. 1401-1449
    • Holm, R.H.1
  • 21
    • 84954703196 scopus 로고
    • For examples of reductions of phosphine oxides by metal hydrides, see
    • For examples of reductions of phosphine oxides by metal hydrides, see: Hein, F.; Issleib, K.; Rabold, H. Z. Anorg. Allg. Chem. 1956, 287, 208-213
    • (1956) Z. Anorg. Allg. Chem. , vol.287 , pp. 208-213
    • Hein, F.1    Issleib, K.2    Rabold, H.3
  • 25
    • 84889187668 scopus 로고
    • For examples of reductions of phosphine oxides by silanes, see
    • For examples of reductions of phosphine oxides by silanes, see: Fritzsche, H.; Hasserodt, U.; Korte, F. Chem. Ber. 1964, 97, 1988-1993
    • (1964) Chem. Ber. , vol.97 , pp. 1988-1993
    • Fritzsche, H.1    Hasserodt, U.2    Korte, F.3
  • 28
    • 0028265318 scopus 로고
    • For examples of reductions of phosphine oxides by Ti(IV)/siloxane, see
    • For examples of reductions of phosphine oxides by Ti(IV)/siloxane, see: Coumbe, T.; Lawrence, N. J.; Muhammad, F. Tetrahedron Lett. 1994, 35, 625-628
    • (1994) Tetrahedron Lett. , vol.35 , pp. 625-628
    • Coumbe, T.1    Lawrence, N.J.2    Muhammad, F.3
  • 30
    • 0000281383 scopus 로고
    • For examples of the stability of alkyl, ketal, and silyl peroxides toward hydride reduction, see
    • For examples of the stability of alkyl, ketal, and silyl peroxides toward hydride reduction, see: Dussault, P.; Sahli, A.; Westermeyer, T. J. Org. Chem. 1993, 58, 5469-5474
    • (1993) J. Org. Chem. , vol.58 , pp. 5469-5474
    • Dussault, P.1    Sahli, A.2    Westermeyer, T.3
  • 44
    • 33947489975 scopus 로고
    • For examples and studies of phosphines and phosphites reacting with dialkyl peroxides, see
    • For examples and studies of phosphines and phosphites reacting with dialkyl peroxides, see: Denney, D. B.; Relles, H. M. J. Am. Chem. Soc. 1964, 86, 3897-3898
    • (1964) J. Am. Chem. Soc. , vol.86 , pp. 3897-3898
    • Denney, D.B.1    Relles, H.M.2
  • 47
    • 33845557937 scopus 로고
    • references cited therein
    • Balci, M. Chem. Rev. 1981, 81, 91-108 and references cited therein
    • (1981) Chem. Rev. , vol.81 , pp. 91-108
    • Balci, M.1
  • 54
    • 0024991476 scopus 로고
    • Peroxyketals are stable to phosphines in the presence of ozonides at low temperature
    • Peroxyketals are stable to phosphines in the presence of ozonides at low temperature: Dussault, P.; Sahli, A. Tetrahedron Lett. 1990, 31, 5117-5120
    • (1990) Tetrahedron Lett. , vol.31 , pp. 5117-5120
    • Dussault, P.1    Sahli, A.2
  • 58
    • 4243845123 scopus 로고    scopus 로고
    • Heating peroxy ketal 1d in the absence of reducing agents also resulted in decomposition, presumably by homolytic decomposition of the oxygen-oxygen bond. See
    • Heating peroxy ketal 1d in the absence of reducing agents also resulted in decomposition, presumably by homolytic decomposition of the oxygen-oxygen bond. See: Helgorsky, C.; Bevilacqua, M.; Degueil-Castaing, M.; Maillard, B. Thermochim. Acta 1997, 297, 93-100
    • (1997) Thermochim. Acta , vol.297 , pp. 93-100
    • Helgorsky, C.1    Bevilacqua, M.2    Degueil-Castaing, M.3    Maillard, B.4
  • 67
    • 77955155492 scopus 로고    scopus 로고
    • Although this study has focused on using triphenylphosphine as the peroxide reductant, we have observed that other alkyl- and arylphosphines behave with equal efficiency. For sterically hindered phosphines, e.g., tricyclohexylphosphine, the use of smaller alkyl trimethylsilyl peroxides is required for efficient conversions
    • Although this study has focused on using triphenylphosphine as the peroxide reductant, we have observed that other alkyl- and arylphosphines behave with equal efficiency. For sterically hindered phosphines, e.g., tricyclohexylphosphine, the use of smaller alkyl trimethylsilyl peroxides is required for efficient conversions.
  • 68
    • 84855620595 scopus 로고    scopus 로고
    • 2)-silane could also be the active reductant. For a discussion, see: Reference 11b
    • 2)-silane could also be the active reductant. For a discussion, see: Reference 11b.
  • 72
    • 1842818692 scopus 로고
    • Titanium(IV) hydrides have been proposed in the reaction between titanium(IV) alkoxides and silanes/siloxanes; see
    • Titanium(IV) hydrides have been proposed in the reaction between titanium(IV) alkoxides and silanes/siloxanes; see: Albizzati, E.; Abis, L.; Pettenati, E.; Giannetti, E. Inorg. Chim. Acta 1986, 120, 197-203
    • (1986) Inorg. Chim. Acta , vol.120 , pp. 197-203
    • Albizzati, E.1    Abis, L.2    Pettenati, E.3    Giannetti, E.4
  • 73
    • 77955126351 scopus 로고    scopus 로고
    • Reference 11
    • Reference 11.
  • 74
    • 0001134624 scopus 로고
    • For examples of Ti(IV) hydrides without cyclopentyldienyl ligands, see
    • For examples of Ti(IV) hydrides without cyclopentyldienyl ligands, see: Cummins, C. C.; Schrock, R. R.; Davis, W. M. Organometallics 1992, 11, 1452-1454
    • (1992) Organometallics , vol.11 , pp. 1452-1454
    • Cummins, C.C.1    Schrock, R.R.2    Davis, W.M.3
  • 80
    • 0001124137 scopus 로고
    • Treatment of cyclopentyldienyltitanium(IV) compounds with silanes has resulted in EPR active products; see
    • Treatment of cyclopentyldienyltitanium(IV) compounds with silanes has resulted in EPR active products; see: Samuel, E.; Harrod, J. F. J. Am. Chem. Soc. 1984, 106, 1859-1860
    • (1984) J. Am. Chem. Soc. , vol.106 , pp. 1859-1860
    • Samuel, E.1    Harrod, J.F.2
  • 85
    • 77955144232 scopus 로고    scopus 로고
    • The amount of paramagnetic species was not quantified
    • The amount of paramagnetic species was not quantified.
  • 92
    • 0036838929 scopus 로고    scopus 로고
    • references cited therein
    • Hoskin, A. J.; Stephan, D. W. Coord. Chem. Rev. 2002, 233-234, 107-129 and references cited therein
    • (2002) Coord. Chem. Rev. , vol.233-234 , pp. 107-129
    • Hoskin, A.J.1    Stephan, D.W.2
  • 95
    • 72449201530 scopus 로고    scopus 로고
    • Based on a detailed mechanistic analysis on the reduction of phosphine oxides by titanium(IV) alkoxides and siloxanes, a titanium(IV) species has been proposed to serve as a one-electron reductant
    • Based on a detailed mechanistic analysis on the reduction of phosphine oxides by titanium(IV) alkoxides and siloxanes, a titanium(IV) species has been proposed to serve as a one-electron reductant: Petit, C.; Favre-Reguillon, A.; Albela, B.; Bonneviot, L.; Mignani, G.; Lemaire, M. Organometallics 2009, 28, 6379-6382
    • (2009) Organometallics , vol.28 , pp. 6379-6382
    • Petit, C.1    Favre-Reguillon, A.2    Albela, B.3    Bonneviot, L.4    Mignani, G.5    Lemaire, M.6
  • 99
    • 1542723511 scopus 로고
    • For earlier studies of O-O bond formation through alkoxy radicals, see:;, and additional references cited in ref 15b,15c
    • For earlier studies of O-O bond formation through alkoxy radicals, see: Koenig, T.; Deinzer, M. J. Am. Chem. Soc. 1966, 88, 4518-4520 and additional references cited in ref 15b,15c
    • (1966) J. Am. Chem. Soc. , vol.88 , pp. 4518-4520
    • Koenig, T.1    Deinzer, M.2
  • 100
    • 77955139141 scopus 로고    scopus 로고
    • Details are provided as Supporting Information
    • Details are provided as Supporting Information.
  • 105
    • 77955155014 scopus 로고    scopus 로고
    • Reference 18c
    • Reference 18c.
  • 115
    • 0035114591 scopus 로고    scopus 로고
    • references cited therein
    • Liu, X.; Verkade, J. G. Heteroat. Chem. 2001, 12, 21-26 and references cited therein
    • (2001) Heteroat. Chem. , vol.12 , pp. 21-26
    • Liu, X.1    Verkade, J.G.2
  • 116
    • 77955140428 scopus 로고    scopus 로고
    • Authentic samples of the crossover products 31 and 32 were prepared for comparison purposes. Details are provided as Supporting Information
    • Authentic samples of the crossover products 31 and 32 were prepared for comparison purposes. Details are provided as Supporting Information.
  • 119
    • 61349185643 scopus 로고    scopus 로고
    • Rappoport Z. Details on experimental procedures, handling, and purifying organic peroxides are provided in the Supporting Information. Although no difficulties were observed in handling and purifying organic peroxides in this report, organic peroxides are potentially explosive
    • Details on experimental procedures, handling, and purifying organic peroxides are provided in the Supporting Information. Although no difficulties were observed in handling and purifying organic peroxides in this report, organic peroxides are potentially explosive: Zabicky, J. In The Chemistry of Peroxides; Rappoport, Z., Ed.; Wiley: Chichester, UK, 2006; Vol. 2, Chapter 7, pp 597 - 774.
    • (2006) The Chemistry of Peroxides , vol.2 , pp. 597
    • Zabicky, J.1


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