10.1002/anie.201811380
Angewandte Chemie International Edition
Tada, Y. Sakai, Y. Ohki, J. Am. Chem. Soc. 2017, 139, 5596-5606;
f) A. Monfredini, V. Santacroce, L. Marchiò, R. Maggi, F. Bigi, G.
Maestri, M. Malacria, ACS Sustainable Chem. Eng. 2017, 5, 8205-
8212.
a) J. M. B. S. J. Lippard, Principles of Bioinorganic Chemistry,
University Science Books, Mill Valley, CA, 1994; b) R. H. Holm,
P. Kennepohl, E. I. Solomon, Chem. Rev. 1996, 96, 2239-2314.
For recent review, see: a) M. Shibasaki, M. Kanai, S. Matsunaga,
N. Kumagai, Acc. Chem. Res. 2009, 42, 1117–1127; b) M.
Delferro, T. J. Marks, Chem. Rev. 2011, 111, 2450-2485.
a) K. J. Bonney, F. Proutiere, F. Schoenebeck, Chem. Sci. 2013, 4,
4434-4439; b) I. Kalvet, K. J. Bonney, F. Schoenebeck, J. Org.
Chem. 2014, 79, 12041-12046; c) M. Aufiero, T. Scattolin, F.
Proutière, F. Schoenebeck, Organometallics 2015, 34, 5191-5195;
d) M. Aufiero, T. Sperger, A. S. Tsang, F. Schoenebeck, Angew.
Chem. Int. Ed. 2015, 54, 10322-10326; e) G. Yin, I. Kalvet, F.
Schoenebeck, Angew. Chem. Int. Ed. 2015, 54, 6809-6813; f) T.
Sperger, C. K. Stirner, F. Schoenebeck, Synthesis 2017, 49, 115-
120; g) I. Kalvet, G. Magnin, F. Schoenebeck, Angew. Chem. Int.
Ed. 2017, 56, 1581-1585; h) I. Kalvet, T. Sperger, T. Scattolin, G.
Magnin, F. Schoenebeck, Angew. Chem. Int. Ed. 2017, 56, 7078-
7082; i) T. Sperger, F. Schoenebeck, Synthesis 2018, DOI:
10.1055/s-0037-1610087; j) S. T. Keaveney, G. Kundu, F.
Schoenebeck, Angew. Chem. Int. Ed. 2018, 57, 12573-12577; k) T.
Scattolin, E. Senol, G. Yin, Q. Guo, F. Schoenebeck, Angew.
Chem. Int. Ed. 2018, 57, 12425-12429.
catalysis, see: d) K. Lin, R. J. Wiles, C. B. Kelly, G. H. M. Davies,
G. A. Molander, ACS Catal. 2017, 7, 5129-5133; for selective C-
SeCF3 bond formation, see: e) A. B. Dürr, H. C. Fisher, I. Kalvet,
K. N. Truong, F. Schoenebeck, Angew. Chem. Int. Ed. 2017, 56,
13431-13435.
[2]
[10]
[11]
See Supporting Information for more examples.
Aside from the presented C-I over C-Br selectivity, there is also
selectivity over triflates: our tests with trimer 2 to site-selectively
couple C-I over C-OTf in 4-iodophenyl triflate with PhMgCl gave
exclusive coupling at the C-I site (68% isolated yield), along with
some consumption of starting material due to metal halogen
exchange side reaction.
M. Rottländer, L. Boymond, L. Berillon, A. Lepreetre, G. Varchi,
S. Avolio, H. Laaziri, G. Queguiner, A. Ricci, G. Cahiez, P.
Knochel, Chem. Eur. J. 2000, 6, 767-770.
This observation appears consistent with higher propensity for
metal/halogen exchange for aryl halides with electron-
withdrawing groups in ortho-position, see: L. Shi, Y. Chu,
P.Knochel. H. Mayr, J. Org. Chem. 2009, 74, 2760-2764.
Pd nanoparticles were generated in situ by heating a solution of
1.5 mol% Pd2dba3 (0.0015 mmol) in toluene to 80 °C for 2 h under
argon atmosphere prior to addition of the cross-coupling partners
at room temperature. See Supporting Information for details.
Gaussian 09, Revision D.01, M. J. Frisch et al., Gaussian Inc.,
Wallingford CT, 2013. (See Supporting Information for full
reference and additional computational information.)
[3]
[4]
[12]
[13]
[14]
[15]
[16]
[5]
[6]
See Supporting Information for detailed discussion.
Recent studies of the oxidative addition step with Pd(0)Ln indicated
barriers around 30 kcal mol-1 for typical room temperature
transformations: a) C. L. McMullin, J. Jover, J. N. Harvey, N. Fey,
Dalton Trans. 2010, 39, 10833-10836; b) C. L. McMullin, N. Fey,
J. N. Harvey, Dalton Trans. 2014, 43, 13545; c) E. Lyngvi, I. A.
Sanhueza, F. Schoenebeck, Organometallics 2015, 34, 805-812.
For a general overview of the use of computational tools for
reactivity studies (and remaining challenges), see: a) C. Poree, F.
Schoenebeck, Acc. Chem. Res. 2017, 50, 605; b) T. Sperger, H. C.
Fisher, F. Schoenebeck, WIREs Comput. Mol. Sci. 2016, 6, 226; c)
T. Sperger, I. A. Sanhueza, I. Kalvet, F. Schoenebeck, Chem. Rev.
2015, 115, 9532; d) A. S.-K. Tsang, I. A. Sanhueza, F.
Schoenebeck, Chem. Eur. J. 2014, 20, 16432.
a) G. W. Bushnell, K. R. Dixon, P. M. Moroney, A. D. Rattray, C.
E. Wan, J. Chem. Soc. Chem. Commun. 1977, 709-710; b) S. J.
Cartwright, K. R. Dixon, A. D. Rattray, Inorg. Chem. 1980, 19,
1120-1124; c) D. M. P. Mingos, R. Vilar, J. Organomet. Chem.
1998, 557, 131-142; d) K. R. Dixon, A. D. Rattray, Inorg. Chem.
2002, 17, 1099-1103; e) L. B. Belykh, T. V. Goremyka, S. V.
Zinchenko, A. V. Rokhin, G. V. Ratovskii, F. K. Schmidt, Russ. J.
Coord. Chem. 2002, 28, 664-670; f) V. Bonuccelli, T. Funaioli, P.
Leoni, F. Marchetti, L. Marchetti, Inorg. Chem. 2013, 52, 8759-
8769; g) S. Blanchard, L. Fensterbank, G. Gontard, E. Lacote, G.
Maestri, M. Malacria, Angew. Chem. Int. Ed. 2014, 53, 1987-1991.
Pd trimers were reported to act as precatalyst in the semi-reduction
of alkynes: a) P.-A. Deyris, T. Cañeque, Y. Wang, P. Retailleau, F.
Bigi, R. Maggi, G. Maestri, M. Malacria, ChemCatChem 2015, 7,
3266-3269; b) A. Monfredini, V. Santacroce, P. A. Deyris, R.
Maggi, F. Bigi, G. Maestri, M. Malacria, Dalton Trans. 2016, 45,
15786-15790; see also Ref. 1c); as catalyst in cycloisomerization
of terminal 1,6-enynes and internal dienynes to tricyclic
cyclohexenes: c) M. Lanzi, T. Cañeque, L. Marchiò, R. Maggi, F.
Bigi, M. Malacria, G. Maestri, ACS Catal. 2017, 8, 144-147; as
components in heterogenous titanate nanotube-supported catalysts
applied in the oxidation of alcohols: d) Y. Yun, H. Sheng, J. Yu, L.
Bao, Y. Du, F. Xu, H. Yu, P. Li, M. Zhu, Adv. Synth. Catal. 2018,
DOI 10.1002/adsc.201800603; and as pre-catalyst in Suzuki
couplings: e) F. Fu, J. Xiang, H. Cheng, L. Cheng, H. Chong, S.
Wang, P. Li, S. Wei, M. Zhu, Y. Li, ACS Catal. 2017, 7, 1860-
1867. However, except for c), no clear differences in reactivity
compared to mononuclear counterparts were showcased in these
cases. For a Pd trimer as off-cycle species, see: f) X. Y. Deng, J.
H. Lin, J. C. Xiao, Org. Lett. 2016, 18, 4384-4387. For a Pd trimer
as precursor to nanoparticle catalysis, see: g) I. Błaszczyk, A.
Gniewek, A. M. Trzeciak, J. Organomet. Chem. 2012, 710, 44-52.
Full conversion of para-iodo acteophenone to the respective para-
diphenylphosphino-acetophenone was observed within 4 h at room
temperature. See Supporting Information for details.
[17]
[7]
[8]
[9]
There are few examples of C-I selective Kumada or Negishi
couplings for selected, specific substrates: a) C. A. Merlic, W. M.
Roberts, Tetrahedron Lett. 1993, 34, 7379-7382 (arylations on 1-
bromo-2-iodobenzene); b) B. Betzemeier, P. Knochel, Angew.
Chem. Int. Ed. Engl. 1997, 36, 2623-2624 (two examples of
Negishi-type arylations of 4a); c) R. Martin, S. L. Buchwald, J.
Am. Chem. Soc. 2007, 129, 3844-3845 (one Kumada-type arylation
of 4a); d) Y. Shimada, R. Haraguchi, S. Matsubara, Synlett 2015,
26, 2395-2398 (two examples for Negishi-type methylation).
Furthermore, there are two reports about Ni-catalyzed C-I selective
functionalization. For selective alkylation by Ni/photoredox dual
4
This article is protected by copyright. All rights reserved.