Organometallics
ARTICLE
transferring the ligand properties to the opposite moiety. Ac-
cording to the HSAB concept various affinities toward a chosen
nucleophile will result, allowing for a classification of ligands
without performing actual experiments. Despite intuition, the
natural charges at C1 do not exhibit any correlation to reaction
rate and stay remarkably constant upon ligand change, whereas
Chem., Int. Ed. 2007, 46, 2284–2287. For halogen electrophiles, see:
(f) Buzas, A.; Gagosz, F. Org. Lett. 2006, 8, 515–518. (g) Yu, M.; Zhang,
G.; Zhang, L. Org. Lett. 2007, 9, 2147–2150. (h) Hashmi, A. S. K.;
Ramamurthi, T. D.; Rominger, F. J. Organomet. Chem. 2009, 694,
592–597. (i) Gockel, B.; Krause, N. Eur. J. Org. Chem. 2010, 311–316.
(j) Weyrauch, J. P.; Hashmi, A. S. K.; Schuster, A.; Hengst, T.; Schetter,
S.; Littmann, A.; Rudolph, M.; Hamzic, M.; Visus, J.; Rominger, F.; Frey,
W.; Bats, J. W. Chem. Eur. J. 2010, 16, 956–963. (k) Hashmi, A. S. K.;
Ramamurthi, T. D.; Tsang, A. S.-K.; Graf, K. Aust. J. Chem. 2010, 63,
1619–1626.
(6) (a) Shi, Y.; Ramgren, S. D.; Blum, S. A. Organometallics 2009,
28, 1275–1277. (b) Hashmi, A. S. K.; Lothsch€utz, C.; D€opp, R.;
Rudolph, M.; Ramamurthi, T. D.; Rominger, F. Angew. Chem. 2009,
121, 8392–8395. Angew. Chem., Int. Ed. 2009, 48, 8243–8246. (c) Shi,
Y.; Roth, K. E.; Ramgren, S. D.; Blum, S. A. J. Am. Chem. Soc. 2009,
131, 18022–18023. (d) Hashmi, A. S. K.; D€opp, R.; Lothsch€utz, C.;
Rudolph, M.; Riedel, D.; Rominger, F. Adv. Synth. Catal. 2010,
352, 1307–1314. (e) Pena-Lꢀopez, M.; Ayꢀan-Varela, M.; Sarandeses,
L. A.; Sestelo, J. P. Chem. Eur. J. 2010, 16, 9905–9909. For a short review
about cross-coupling reactions involving gold, see also: (f) Garcia, P.;
Malacria, M.; Aubert, C.; Gandon, V.; Fensterbank, L. ChemCatChem
2010, 2, 493–497.
1
the H NMR of the hydrogen atom bound to C4 is noticeably
influenced by the varying electronic ligand properties.
’ ASSOCIATED CONTENT
S
Supporting Information. Text, figures, tables, and CIF
b
files giving experimental details, characterization data, crystal-
lographic data, and details of the calculations. This material is
’ AUTHOR INFORMATION
Corresponding Author
*M.P.: tel, +49(0)6221-545208; fax, +49(0)6221-545221;
e-mail, markus.pernpointner@pci.uni-heidelberg.de. A.S.K.H.:
tel, +49(0)6221-548413; fax, +49(0)6221-544205; e-mail, hashmi@
hashmi.de.
(7) (a) Hashmi, A. S. K. Angew. Chem. 2008, 120, 6856–6858.
Angew. Chem., Int. Ed. 2008, 47, 6754–6756. (b) Echavarren, A. M.
Nature Chem. 2009, 1, 431–433.
(8) (a) F€urstner, A.; Morency, L. Angew. Chem. 2008, 120, 5108–
5111. Angew. Chem., Int. Ed. 2008, 47, 5030–5033. (b) Seidel, G.; Mynott,
R.; F€urstner, A. Angew. Chem. 2009, 121, 2548–2551. Angew. Chem., Int. Ed.
2009, 48, 2510–2513.
(9) Benitez, D.; Shapiro, N. D.; Tkatchouk, E.; Wang, Y.; Goddard,
W. A., III; Toste, F. D. Nature Chem. 2009, 1, 482–486.
’ ACKNOWLEDGMENT
This work was supported by the Deutsche Forschungsge-
meinschaft (SFB 623) and by Umicore AG & Co. KG. C.L. is
grateful for a grant of the Studienstiftung des dt. Volkes e.V.,
Petra Kr€amer is gratefully acknowledged for the countless NMR
experiments.
(10) The corresponding NMR spectra can be found in the Support-
ing Information.
(11) 18O labeling was 88% for 5e-OTf, 91% for 5a-OTf, and 55% for
5g-OTf (97% 18O-labeled water), respectively. The small ratio of
labeling for 5g-OTf can be traced back to incomplete conversion of
5g-OTf to 6g under the reaction conditions and partial hydrolysis during
workup. 3-Methyl-5-(propan-2-yl)furan-2(5H)-one, which was formed
as a byproduct under reaction conditions by protodemetalation of 6g,
shows an 18O labeling of 85%.
’ REFERENCES
(1) For reviews on gold catalysis, see: (a) Hashmi, A. S. K.; Hutchings,
G. J. Angew. Chem. 2006, 118, 8064–8105. Angew. Chem., Int. Ed. 2006,
45, 7896–7936. (b) F€urstner, A.; Davis, P. W. Angew. Chem. 2007,
119, 3478–3519. Angew. Chem., Int. Ed. 2007, 46, 3410–3449. (c) Hashmi,
A. S. K. Chem. Rev. 2007, 107, 3180–3211. (d) Arcadi, A. Chem. Rev. 2008,
108, 3266–3325. (e) Jimꢀenez-Nꢀunez, E.; Echavarren, A. M. Chem. Rev.
2008, 108, 3326–3350. (f) Li, Z. G.; Brouwer, C.; He, C. Chem. Rev. 2008,
108, 3239–3265. (g) Gorin, D. J.; Sherry, B. D.; Toste, F. D. Chem. Rev.
2008, 108, 3351–3378. (h) Hashmi, A. S. K.; B€uhrle, M. Aldrichim. Acta
2010, 43, 27–33. (i) Hashmi, A. S. K.; Rudolph, M. Chem. Commun. 2011,
47, 6536–6544.
(2) Hashmi, A. S. K. Angew. Chem. 2010, 122, 5360–5369. Angew.
Chem., Int. Ed. 2010, 49, 5232–5241.
(3) (a) Liu, L.-P.; Xu, B.; Mashuta, M. S.; Hammond, G. B. J. Am.
Chem. Soc. 2008, 130, 17642–17643. (b) Liu, L.-P.; Hammond, G. B.
Chem. Asian J. 2009, 4, 1230–1236.
(4) (a) Weber, D.; Tarselli, M. A.; Gagnꢀe, M. R. Angew. Chem. 2009,
121, 5843–5846. Angew. Chem., Int. Ed. 2009, 48, 5733–5736. (b)
Hashmi, A. S. K.; Schuster, A.; Rominger, F. Angew. Chem. 2009,
121, 8396–8398. Angew. Chem., Int. Ed. 2009, 48, 8247–8249. (c) Zeng,
X.; Kinjo, R.; Donnadieu, B.; Bertrand, G. Angew. Chem. 2010,
122, 954–957. Angew. Chem., Int. Ed. 2010, 49, 942–945. (d) Hashmi,
A. S. K.; Ramamurthi, T. D.; Rominger, F. Adv. Synth. Catal. 2010,
352, 971–975. (e) Hashmi, A. S. K. Gold Bull. 2009, 42, 275–279.
(5) For carbon electrophiles, see: (a) Zhang, L. J. Am. Chem. Soc.
2005, 127, 16804–16805. (b) Nakamura, I.; Sato, T.; Yamamoto, Y.
Angew. Chem. 2006, 118, 4585–4587. Angew. Chem., Int. Ed. 2006, 45,
4473–4475. (c) Dubꢀe, P.; Toste, F. D. J. Am. Chem. Soc. 2006,
128, 12062–12063. For silicon electrophiles, see: (d) Nakamura, I.;
Sato, T.; Terada, M.; Yamamoto, Y. Org. Lett. 2007, 9, 4081–4083. For
sulfur electrophiles, see: (e) Nakamura, I.; Yamagishi, U.; Song, D.;
Konta, S.; Yamamoto, Y. Angew. Chem. 2007, 119, 2334–2337. Angew.
(12) (a) Asao, N.; Alkawa, H.; Tago, S.; Umetsu, K. Org. Lett. 2007,
9, 4299–4302. See also: (b) Zhang, Q.; Sung, J.; Zhu, Y.; Zhang, F.; Yu,
B. Angew. Chem. 2011, 123, 5035–5038. Angew. Chem., Int. Ed. 2011,
50, 4933–4936. For the isolation of the corresponding vinylgold(I)
species, see: (c) Zhu, Y.; Yu, B. Angew. Chem. 2011, 123, 8479–8482;
Angew. Chem., Int. Ed. 2011, 50, 8329–8332.
(13) For the synthesis and catalytic activity of gold(I) triflimidate
complexes, see: (a) Mꢀezailles, N.; Ricard, L.; Gagosz, F. Org. Lett. 2005,
7, 4133–4136. (b) Ricard, L.; Gagosz, F. Organometallics 2007, 26,
4704–4707.
(14) For the synthesis of NAC gold(I) complexes from the corre-
sponding isonitrile complexes and their use in catalysis, see: (a)
Bartolomꢀe, C.; Ramiro, Z.; García-Cuadrado, D.; Pꢀerez-Galꢀan, P.;
Raducan, M.; Bour, C.; Echavarren, A. M.; Espinet, P. Organometallics
2010, 29, 951–956. (b) Hashmi, A. S. K.; Hengst, T.; Lothsch€utz, C.;
Rominger, F. Adv. Synth. Catal. 2010, 352, 1315–1337. For an extension
of this principle to the synthesis of NHCs, see: (c) Hashmi, A. S. K.;
Lothsch€utz, C.; B€ohling, C.; Hengst, T.; Hubbert, C.; Rominger, F. Adv.
Synth. Catal. 2010, 352, 3001–3012. (d) Hashmi, A. S. K.; Lothsch€utz,
C.; Graf, K.; H€affner, T.; Schuster, A.; Rominger, F. Adv. Synth. Catal.
2011, 354, 1407–1412.
(15) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.;
Robb, M. A.; Cheeseman, J. R.; Montgomery, Jr., J. A.; Vreven, T.;
Kudin, K. N.; Burant, J. C.; Millam, J. M.; Iyengar, S. S.; Tomasi, J.;
Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson,
G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.;
Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.;
Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Bakken, V.;
5902
dx.doi.org/10.1021/om200735c |Organometallics 2011, 30, 5894–5903