Journal of the American Chemical Society
Article
(19) Itami, K.; Nokami, T.; Ishimura, Y.; Mitsudo, K.; Kamei, T.;
Yoshida, J.-i. J. Am. Chem. Soc. 2001, 123, 11577−11585.
(20) Li, C.-J. Chem. Rev. 2005, 105, 3095−3166. Li, C.-J.; Chen, L.
Chem. Soc. Rev. 2006, 35, 68−82. Li, C.-J.; Chan, T.-H. Comprehensive
Organic Reactions in Aqueous Media; 2nd ed.; Wiley-InterScience:
Hoboken, NJ, 2007.
(42) Hosoi, K.; Nozaki, K.; Hiyama, T. Proc. Jpn. Acad., Ser. B 2002,
78, 154−160. Jeffery, T.; Ferber, B. Tetrahedron Lett. 2003, 44, 193−
197. Denmark, S. E.; Tymonko, S. A. J. Am. Chem. Soc. 2005, 127,
8004−8005. Sore, H. F.; Boehner, C. M.; Laraia, L.; Logoteta, P.;
Prestinari, C.; Scott, M.; Williams, K.; Galloway, W. R. J. D.; Spring, D.
R. Org. Biomol. Chem. 2011, 9, 504−515. See also: Joucla, L.; Cusati,
G.; Pinel, C.; Djakovitch, L. Adv. Synth. Catal. 2010, 352, 1993−2001.
(43) For a review on the hydrolysis of alkoxysilanes and the
condensation of silanolates, see: Brinker, C. J. J. Non-Cryst. Solids 1988,
100, 31−50.
(44) Especially designed pentacoordinate silicon species can be stable
in water: Tacke, R.; Bertermann, R.; Burschka, C.; Dragota, S. Angew.
Chem., Int. Ed. 2005, 44, 5292−5295. Couzijn, E. P. A.; Ehlers, A. W.;
Schakel, M.; Lammertsma, K. J. Am. Chem. Soc. 2006, 128, 13634−
13639.
(21) Metal-Catalyzed Reactions in Water; Dixneuf, P., Cadierno, V.,
Eds.; Wiley-VCH: Weinheim, Germany, 2013. Aqueous-Phase Organo-
metallic Catalysis: Concepts and Applications, 2nd ed.; Cornils, B.,
Herrman, W. A., Eds.; Wiley-VCH: Weinheim, Germany, 2004.
Shaughnessy, K. H. Chem. Rev. 2009, 109, 643−710.
(22) Blackmond, D. G.; Armstrong, A.; Coombe, V.; Wells, A. Angew.
Chem., Int. Ed. 2007, 46, 3798−3800.
(23) Xue, L.; Lin, Z. Chem. Soc. Rev. 2010, 39, 1692−1705.
(24) Siegbahn, P. E. M.; Stromberg, S.; Zetterberg, K. Organometallics
̈
(45) For studies on the alkaline hydrolysis of RSi(OR′)3 species, see:
Pozdnyakova, Y. A.; Korlyukov, A. A.; Lyssenko, K. A.; Zherlitsyna, L.;
Auner, N.; Shchegolikhina, O. I. J. Organomet. Chem. 2013, 729, 86−
94. Pozdniakova, Y. A.; Lyssenko, K. A.; Korlyukov, A. A.;
Blagodatskikh, I. V.; Auner, N.; Katsoulis, D.; Shchegolikhina, O. I.
Eur. J. Inorg. Chem. 2004, 1253−1261.
1996, 15, 5542−5550. Albert, K.; Gisdakis, P.; Rosch, N. Organo-
̈
metallics 1998, 17, 1608−1616. Sundermann, A.; Uzan, O.; Martin, J.
M. L. Chem.Eur. J. 2001, 7, 1703−1711. Deeth, R. J.; Smith, A.;
Brown, J. M. J. Am. Chem. Soc. 2004, 126, 7144−7151. Kozuch, S.;
Shaik, S. J. Am. Chem. Soc. 2006, 128, 3355−3365. Surawatanawong,
P.; Hall, M. B. Organometallics 2008, 27, 6222−6232. Backtorp, C.;
̈
(46) Parr, R. G.; Pearson, R. G. J. Am. Chem. Soc. 1983, 105, 7512−
7516.
Norrby, P.-O. J. Mol. Catal. A: Chem. 2010, 328, 108−113. Wucher, P.;
Caporaso, L.; Roesle, P.; Ragone, F.; Cavallo, L.; Mecking, S.; Gottker-
̈
(47) We arrived at a similar conclusion in a parallel study with
trimethoxyphenylsilane. This means that the cross-coupling reactions
between aryltrialkoxysilanes and aryl halides described by several
groups (refs 29−32) almost certainly follow a Denmark-type
activation. See Table S2 in the Supporting Information.
(48) The kinetics of this reaction is slow at temperatures below 100
°C. Thus, an isolated and purified sample of 32 afforded quantitatively
(E)-31-d1 in deuterated water at pH ≈ 12 and 140 °C in around 4 h.
Hydrolysis was not observed after 24 h at 80 °C and only partially at
100 °C.
Schnetmann, I. Proc. Natl. Acad. Sci. U.S.A. 2011, 108, 8955−8959.
Backtorp, C.; Norrby, P.-O. Dalton Trans. 2011, 40, 11308−11314.
Skold, C.; Kleimark, J.; Trejos, A.; Odell, L. R.; Nilsson Lill, S. O.;
̈
Norrby, P.-O.; Larhed, M. Chem.Eur. J. 2012, 18, 4714−4722.
(25) See, for instance: Rossin, A.; Kovac
́
s, G.; Ujaque, G.; Lledos
́
, A.;
Jo, F. Organometallics 2006, 25, 5010−5023. Kovac
Gonsalvi, L.; Lledos, A.; Peruzzini, M. Organometallics 2010, 29,
5121−5131. Vilella, L.; Vidossich, P.; Balcells, D.; Lledos, A. Dalton
Trans. 2011, 40, 11241−11247. Bellarosa, L.; Díez, J.; Gimeno, J.;
Lledos, A.; Suar
ez, F. J.; Ujaque, G.; Vicent, C. Chem.Eur. J. 2012,
18, 7749−7765.
(26) Comas-Vives, A.; Stirling, A.; Lledos
Eur. J. 2010, 16, 8738−8747. Kovacs, G.; Stirling, A.; Lledos
́
s, G.; Rossin, A.;
́
́
́
́
(49) See the Introduction for references on the dual Heck−Hiyama
́
reactivity in vinylsilanes. Other references: Albeniz, A. C.; Espinet, P.;
́
, A.; Ujaque, G. Chem.
, A.;
́
Lopez-Fernandez, R. Organometallics 2006, 25, 5449−5455. Alvisi, D.;
́
́
Blart, E.; Bonini, B. F.; Mazzanti, G.; Ricci, A.; Zani, P. J. Org. Chem.
1996, 61, 7139−7146.
Ujaque, G. Chem.Eur. J. 2012, 18, 5612−5619.
(27) Ross, A. J.; Dreiocker, F.; Schafer, M.; Oomens, J.; Meijer, A. J.
̈
(50) Hatanaka, Y.; Goda, K.-i.; Hiyama, T. J. Organomet. Chem. 1994,
465, 97−100.
H. M.; Pickup, B. T.; Jackson, R. F. W. J. Org. Chem. 2011, 76, 1727−
1734. Orbach, M.; Choudhury, J.; Lahav, M.; Zenkina, O. V.; Diskin-
Posner, Y.; Leitus, G.; Iron, M. A.; van der Boom, M. E.
Organometallics 2012, 31, 1271−1274.
(28) Huang, T.; Li, C.-J. Tetrahedron Lett. 2002, 43, 403−405.
(29) Wolf, C.; Lerebours, R. Org. Lett. 2004, 6, 1147−1150.
(30) Lerebours, R.; Wolf, C. Synthesis 2005, 2287−2292. Alacid, E.;
(51) Early proposals for anti elimination in alkenylstannanes have
been questioned: Kikukawa, K.; Umekawa, H.; Matsuda, T. J.
Organomet. Chem. 1986, 311, C44−C46. Busacca, C. A.; Swestock,
J.; Johnson, R. E.; Bailey, T. R.; Musza, L.; Rodger, C. A. J. Org. Chem.
1994, 59, 7553−7556. Farina, V.; Azad Hossain, M. Tetrahedron Lett.
1996, 37, 6997−7000. Fillion, E.; Taylor, N. J. J. Am. Chem. Soc. 2003,
125, 12700−12701.
Naj
Jesus, E.; Lop
́
era, C. Adv. Synth. Catal. 2006, 348, 945−952. Gordillo, A.; de
́
ez-Mardomingo, C. Org. Lett. 2006, 8, 3517−3520.
́
(52) Slow reaction rates in Heck reactions have been correlated with
a difficult reductive elimination of HX: Hills, I. D.; Fu, G. C. J. Am.
Chem. Soc. 2004, 126, 13178−13179. See also: Shmidt, A. F.;
Smirnov, V. V. Kinet. Catal. 2001, 42, 800−804.
(53) It was also quite interesting to observe that the Heck coupling
between acrylic acid and 4-iodobenzoic acid was accelerated when the
reaction was performed in the presence of triethoxyvinylsilane despite
the concurrence of the Heck coupling of both olefins with the
iodoarene. This result suggests that the reductive elimination of HX is
a rate-determining step in this reaction. In the presence of
triethoxyvinylsilane, exchange of the coupled olefin by triethoxyvi-
nylsilane on the PdH intermediate, followed by desilylation of the
latter, provides a quicker alternative to classical HX elimination.
(31) Shi, S.; Zhang, Y. J. Org. Chem. 2007, 72, 5927−5930.
(32) Srimani, D.; Sawoo, S.; Sarkar, A. Org. Lett. 2007, 9, 3639−3642.
́
(33) Alacid, E.; Najera, C. Adv. Synth. Catal. 2006, 348, 2085−2091.
́
́
(34) Gordillo, A.; de Jesus, E.; Lopez-Mardomingo, C. Chem.
Commun. 2007, 4056−4058.
(35) Alacid, E.; Najera, C. J. Org. Chem. 2008, 73, 2315−2322.
(36) For the use of organotri(alkoxy)silanes as coupling partners, see:
Tamao, K.; Kobayashi, K.; Ito, Y. Tetrahedron Lett. 1989, 30, 6051−
6054. Handy, C. J.; Manoso, A. S.; McElroy, W. T.; Seganish, W. M.;
DeShong, P. Tetrahedron 2005, 61, 12201−12225.
(37) Hagiwara, E.; Gouda, K.-I.; Hatanaka, Y.; Hiyama, T.
Tetrahedron Lett. 1997, 38, 439−442.
́
(38) Gordillo, A.; de Jesus, E.; Lop
́
ez-Mardomingo, C. J. Am. Chem.
́
(54) Gordillo, A.; Forigua, J.; Lop
Organometallics 2011, 30, 352−355.
(55) TOF values were measured at 20% conversion: Umpierre, A. P.;
́
́
ez-Mardomingo, C.; de Jesus, E.
Soc. 2009, 131, 4584−4585.
(39) The Si−vinyl bond is slowly hydrolyzed under these high-
temperature conditions, with the corresponding formation of ethylene.
de Jesus, E.; Dupont, J. ChemCatChem 2011, 3, 1413−1418.
́
́
(40) Ferre-Filmon, K.; Delaude, L.; Demonceau, A.; Noels, A. F.
(56) This analysis is based on the assumption that the reaction
products are stereoisotopically inert under these reaction conditions.
See the Supporting Information for the description of experiments
performed to rule out the existence of H/D scrambling processes
under these conditions.
Coord. Chem. Rev. 2004, 248, 2323−2336.
(41) Kormos, C. M.; Leadbeater, N. E. J. Org. Chem. 2008, 73, 3854−
3858. Nobre, S. M.; Muniz, M. N.; Seferin, M.; da Silva, W. M.;
Monteiro, A. L. Appl. Organomet. Chem. 2011, 25, 289−293.
N
dx.doi.org/10.1021/ja404255u | J. Am. Chem. Soc. XXXX, XXX, XXX−XXX