Journal of the American Chemical Society
Article
(f) Denmark, S. E.; Regens, C. S. Acc. Chem. Res. 2008, 41, 1486−1499.
(g) Denmark, S. E. J. Org. Chem. 2009, 74, 2915−2927. (h) Denmark, S.
E.; Butler, C. S. Chem. Commun. 2009, 20−33. (i) Denmark, S. E.; Liu, J.
H.-C. Angew. Chem., Int. Ed. 2010, 49, 2978−2986. (j) Denmark, S. E.;
Liu, J. H.-C. Isr. J. Chem. 2010, 50, 577−587. (k) Chang, W.-t. T.; Smith,
R. C.; Regens, C. S.; Bailey, A. D.; Werner, N. S. Org. React. 2011, 75,
213−745. (l) Sore, H. F.; Galloway, W. R. J. D.; Spring, D. R. Chem. Soc.
Rev. 2012, 41, 1845−1866.
1606. (c) Mateo, C.; Fernan
A. M. Organometallics 1998, 17, 3661−3669.
(14) Cotter, W. D.; Barbour, L.; McNamara, K. L.; Hechter, R.;
Lachicotte, R. J. Am. Chem. Soc. 1998, 120, 11016−11017.
(15) Marciniec, B.; Maciejewski, H. Coord. Chem. Rev. 2001, 223, 301−
335.
(16) (a) Fukuoka, A.; Sato, A.; Mizuho, Y.; Hirano, M.; Komiya, S.
Chem. Lett. 1994, 1641−1644. (b) Fukuoka, A.; Sato, A.; Kodama, K.-y.;
Hirano, M.; Komiya, S. Inorg. Chim. Acta 1999, 294, 266−274.
(c) Mintcheva, N.; Nishihara, Y.; Mori, A.; Osakada, K. J. Organomet.
Chem. 2001, 629, 61−67. (d) Mintcheva, N.; Nishihara, Y.; Tanabe, M.;
Hirabayashi, K.; Mori, A.; Osakada, K. Organometallics 2001, 20, 1243−
1246.
(17) Tymonko, S. A.; Smith, R. C.; Ambrosi, A.; Ober, M. H.; Wang,
(following paper in this issue).
́
dez-Rivas, C. J.; Car
́
denas, D.; Echavarren,
(3) Denmark, S. E.; Sweis, R. F. J. Am. Chem. Soc. 2004, 126, 4876−
4882.
(4) For a definition of this atomic classification scheme, see: Perkins, C.
W.; Martin, J. C.; Arduengo, A. J.; Lau, W.; Alegria, A.; Kochi, J. J. Am.
Chem. Soc. 1980, 102, 7753−7759.
(5) (a) Hiyama, T. J. Organomet. Chem. 2002, 653, 58−61. (b) Hiyama,
T. In Metal-Catalyzed, Cross-Coupling Reactions; Diederich, F., Stang, P.
J., Eds.; Wiley-VCH: Weinhein, Germany, 1998; Chapter 10.
(c) Hiyama, T.; Shirakawa, E. Top. Curr. Chem. 2002, 219, 61−85.
(d) Nakao, Y.; Hiyama, T. Chem. Soc. Rev. 2011, 40, 4893−4901.
(6) (a) Farina, V. Adv. Synth. Catal. 2004, 346, 1553−1582.
(b) Bedford, R. B.; Cazin, C. S. J.; Holder, D. Coord. Chem. Rev. 2004,
248, 2283−2321. (c) Assen, E.; Kantchev, B.; O’Brien, C. J.; Organ, M.
(18) Denmark, S. E.; Sweis, R. F. J. Am. Chem. Soc. 2001, 123, 6439−
6440.
(19) Yamashita, M.; Vicario, J. V. C.; Hartwig, J. F. J. Am. Chem. Soc.
2003, 125, 16347−16360.
(20) To assist the reader in identifying the complexes, suffixes have
been appended to compound numbers to designate the ligand: p =
dppp, t = Ph3P.
(21) The crystallographic coordinates of complexes 11p and 11t have
been deposited with the Cambridge Crystallographic Data Centre,
deposition nos. 606765 and 765349, respectively. These data can be
(22) Denmark, S. E.; Smith, R. C. Synlett 2006, 2921−2928.
(23) Denmark, S. E.; Smith, R. C.; Tymonko, S. A. Tetrahedron 2007,
63, 5730−5738.
(24) This rate equation is also consistent with turnover-limiting
reductive elimination. However, reductive elimination is known to be
extremely rapid with palladium; thus, transmetalation remains the only
viable turnover-limiting step. See: Gilles, A.; Stille, J. K. J. Am. Chem. Soc.
1980, 102, 4933−4941.
(25) The addition of 2-bromotoluene (14) as a scavenger was required
to consume dpppPd(0) formed as a byproduct.
(26) (a) Farina, V.; Kapadia, S.; Krishnan, B.; Wang, C.; Liebeskind, L.
S. J. Org. Chem. 1994, 59, 5905−5911. (b) Allred, G. D.; Liebeskind, L. S.
J. Am. Chem. Soc. 1996, 118, 2748−2749.
(27) For these experiment to give interpretable results, 3.3 equiv of aryl
halide had to be added to consume the (dppp)Pd(0) formed as a
stoichiometric byproduct. Experiments without added halide stalled at
low conversion.
(28) A number of control experiments were carried out to eliminate
other possible roles of CuTC: (1) equimolar amounts of CuTC (with
respect to Pd) have no accelerating effect on the rate of the catalytic
reaction (2.68 × 10−2 mM/s vs 3.05 × 10−2 mM/s without CuTC) and
(2) the room-temperature reaction of 11p with 10 mol % of potassium
thienylcarboxylate afforded no product, thus excluding an activating role
of the carboxylate in CuTC.
́
G. Angew. Chem., Int. Ed. 2007, 46, 2768−2813. (d) Díez-Gonzalez, S.;
Nolan, S. P. Coord. Chem. Rev. 2007, 251, 874−883. (e) Surry, D. S.;
Buchwald, S. L. Angew. Chem., Int. Ed. 2008, 47, 6338−6361. (f) Fu, G.
́
C. Acc. Chem. Res. 2008, 41, 1555−1564. (g) Selander, N.; Szabo, K. J.
Chem. Rev. 2011, 111, 2048−2076.
(7) Denmark, S. E.; Ober, M. H. Adv. Synth. Catal. 2004, 346, 1703−
1714.
(8) (a) Fauvarque, J.-F.; Pfluger, F.; Troupel, M. J. Organomet. Chem.
̈
1981, 208, 419−427. (b) Portnoy, M.; Milstein, D. Organometallics
1993, 12, 1655−1664. (c) Vincente, J.; Arcas, A.; Bautista, D.; Jones, P.
Organometallics 1997, 16, 2127−2138. (d) Casado, A.; Espinet, P.
Organometallics 1998, 17, 954−959. (e) Barden, T. E.; Biscoe, M. R.;
Buchwald, S. L. Organometallics 2007, 26, 2183−2192. (f) Biscoe, M. R.;
Fors, B. P.; Buchwald, S. L. J. Am. Chem. Soc. 2008, 130, 6686−6687.
(g) Barrios-Landeros, F.; Carrow, B. P.; Hartwig, J. F. J. Am. Chem. Soc.
2008, 130, 5842−5843. (h) Barrios-Landeros, F.; Carrow, B. P.;
Hartwig, J. F. J. Am. Chem. Soc. 2009, 131, 8141−8154.
(9) (a) Gillie, A.; Stille, J. J. Am. Chem. Soc. 1980, 102, 4933−4941.
(b) Ozawa, F.; Ito, T.; Nakamura, Y.; Yamamoto, A. Bull. Chem. Soc. Jpn.
1981, 54, 1868−1880. (c) Tatsumi, K.; Hoffmann, R.; Yamamoto, A.;
Stille, J. K. Bull. Chem. Soc. Jpn. 1981, 54, 1857−1867. (d) Hartwig, J. F.
Inorg. Chem. 2007, 46, 1936−1947. (e) Perez-Rodriguez, M.; Braga, A.;
́
Garcia-Melchor, M.; Perez-Temprano, M.; Casares, J.; Ujaque, G.; de
Lera, A.; Alvarez, R.; Maseras, F.; Espinet, P. J. Am. Chem. Soc. 2009, 131,
3650−3657.
(10) Denmark, S. E.; Sweis, R. R.; Wehrli, D. J. Am. Chem. Soc. 2004,
126, 4865−4875.
(11) Both computational11a and experimental11b studies have recently
concluded that a hypercoordinated fluorosilicate is not involved in the
transmetalation step for vinyltrimethylsilane and aryltrimethoxysilanes,
respectively. These authors implicate a critical role for an organo-
palladium fluoride complex which combines with the silicon partner in a
turnover-limiting transmetalation. The relevance of these studies to the
mechanism of cross-coupling of silanols is currently under investigation.
(a) Sugiyama, A.; Ohnishi, Y.-y.; Nakaoka, M.; Nakao, Y.; Sato, H.;
Sakaki, S.; Nakao, Y.; Hiyama, T. J. Am. Chem. Soc. 2008, 130, 12975−
12985. (b) Amatore, C.; Grimaud, L.; Le Duc, G.; Jutand, A. Angew.
Chem., Int. Ed. 2014, 53, 6982−6985.
(29) This rate is the average of entries 1−3 in Table 1.
(30) This experiment assumes that the affinity of Cu(I) for phosphine
is sufficiently higher than that of Pd(II) to allow complete sequestering
of the ligand by the Cu(I).
(12) A recently reported mechanistic study (product analysis, isotope
labeling, and computational analysis) found that the aqueous hydroxide-
promoted cross-coupling of aryl halides with vinyltrimethoxysilane
proceeds via a Heck-type reaction followed by a rapid protiodesilylation.
Remarkably, the mechanism changed to a Hiyama-type cross-coupling
in THF. Gordillo, A.; Ortuno, M. A.; Lop
́
ez-Mardomingo, C.; Lledos
́
,
̃
A.; Ujaque, G.; de Jesus, E. J. Am. Chem. Soc. 2013, 135, 13749−13763.
́
(13) (a) Car
Int. Ed. 1994, 33, 2445−2447. (b) Mateo, C.; Car
Fernan
dez-Rivas, C.; Echavarren, A. M. Chem.Eur. J. 1996, 2, 1596−
́
denas, D. J.; Mateo, C.; Echavarren, A. M. Angew. Chem.,
́
denas, D. J.;
́
H
J. Am. Chem. Soc. XXXX, XXX, XXX−XXX