Journal of the American Chemical Society
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(8) Au-catalyzed oxidative 1,2-amino- and oxyarylation of alkenes: (a)
-oxyarylations of ethylene as the basis of a modular entry to homo-
benzylic ethers. Within the context of oxidative Au-catalysis, sev-
eral aspects of this study are of note, including (a) the first examples
of catalytic ethylene functionalization, (b) insights into the elec-
tronic effects of phosphine ligands, (c) the first use of IBA-OTf as
oxidant, and (d) compelling evidence for oxidation prior to
transmetallation in Au-catalyzed alkene 1,2-oxyarylation. From a
broader synthetic perspective, this study provides a rare example of
a catalytic method that enables the differential 1,2-difunctionaliza-
tion of ethylene, establishing this feedstock chemical as an effec-
tive two carbon bis-electrophilic building block.
Zhang, G.; Cui, L.; Wang, Y.; Zhang, L. J. Am. Chem. Soc. 2010,
132, 1474; (b) Melhado, A. D.; Brenzovich, W. E.; Lackner, A. D.;
Toste, F. D. J. Am. Chem. Soc. 2010, 132, 8885; (c) Ball, L. T.;
Green, M.; Lloyd-Jones, G. C.; Russell, C. A. Org. Lett. 2010, 12,
4724; (d) Brenzovich, W. E.; Brazeau, J. F.; Toste, F. D. Org. Lett.
2010, 12, 4728; (e) Tkatchouk, E.; Mankad, N. P.; Benitez, D.; God-
dard III, W. A.; Toste, F. D. J. Am. Chem. Soc. 2011, 133, 14293; (f)
Ball, L. T.; Lloyd-Jones, G. C.; Russell, C. A. Chem. Eur. J. 2012,
18, 2931; (g) Brenzovich Jr, W. E.; Benitez, D.; Lackner, A. D.; Shu-
natona, H. P.; Tkatchouk, E.; Goddard III, W. A.; Toste, F. D., An-
gew. Chem. Int. Ed. 2010, 49, 5519-5522. For mechanistically dis-
tinct processes that employ electrophilic aryl sources, see: (h) Sahoo,
B.; Hopkinson, M. N.; Glorius, F. J. Am. Chem. Soc. 2013, 135,
5505; (i) Hopkinson, M. N.; Sahoo, B.; Glorius, F. Adv. Synth. Catal.
2014, 356, 2794; (j) Dong, B.; Peng, H.; Motika, S. E.; Shi, X. Chem.
Eur. J. 10.1002/chem.201701970.
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ASSOCIATED CONTENT
Supporting Information
Experimental details, characterization data and crystallographic
data. This material is available free of charge via the Internet at
(9) For a review that encompasses activation of π-systems by gold, see:
Brooner, R. E. M.; Widenhoefer, R. A. Angew. Chem. Int. Ed. 2013,
52, 11714.
(10) Although ethylene has been exploited in isohypsic Au(I)-catalysis
(see: (a) Zhang, Z.; Lee, S. D.; Widenhoefer, R. A. J. Am. Chem. Soc.
2009, 131, 5372), its engagement in Au(III)-dependent bond for-
mations has not been achieved outside of stoichiometric processes.
Examples of ethylene functionalization via Au(III)-complexes: (b)
Rezsnyak, C. E.; Autschbach, J.; Atwood, J. D.; Moncho, S. J.
Coord. Chem., 2013, 66, 1153; (c) Langseth, E.; Nova, A.; Tråseth,
E. A.; Rise, F.; Øien, S.; Heyn, R. H.; Tilset, M. J. Am. Chem. Soc.
2014 136, 10104; (d) Holmsen, M. S. M.; Nova, A.; Balcells, D.;
Langseth, E.; Øien-Ødegaard, S.; Tråseth, E. A.; Heyn, R. H.; Tilset,
M. Dalton Trans. 2016 45, 14719; (e) Balcells, D.; Eisenstein, O.;
Tilset, M.; Nova, A. Dalton Trans. 2016 45, 5504.
AUTHOR INFORMATION
Corresponding Authors
john.bower@bris.ac.uk, chris.russell@bris.ac.uk
Notes
The authors declare no competing financial interest
ACKNOWLEDGMENT
(11) We note that the process provides an alternative to challenging anti-
Markovnikov additions of alcohols to styrenes.
M. J. H. thanks the Bristol Chemical Synthesis Centre for Doc-
toral Training, funded by the EPSRC (EP/G036764/1) and Syn-
genta, for a PhD studentship. We thank the Royal Society for a
University Research Fellowship (to J.F.B). The University of Bris-
tol, School of Chemistry X-ray crystallographic service is acknowl-
edged for analysis of 4 and 7.
(12) Conventional bis-electrophilic reagents, such as 1,2-dibromoethane,
suffer from poor reactivity and competing elimination. Other bis-
electrophilic C2 reagents offer increased utility at the expense of
lower atom economy. For example, see: Yar, M.; McGarrigle, E. M.;
Aggarwal, V. K. Angew. Chem. Int. Ed. 2008, 47, 3784.
(13) Further optimization studies are given in the SI, including the evalu-
ation of other oxidants.
(14) (a) Zhdankin, V. V; Kuehl, C. J.; Krasutsky, A. P.; Bolz, J. T.; Si-
monsen, A. J. J. Org. Chem. 1996, 61, 6547; (b) Merritt, E. A.; Ol-
ofsson, B. Eur. J. Org. Chem. 2011, 3690.
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(15) For hydrolytically sensitive systems, acid free conditions were cru-
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2o (65%) under the conditions in Table 1, Entry 8.
(3) A key exception is the use of ethylene in metathesis-type reactions
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(16) (a) Dehydrative dimerization of the alcohol to the corresponding
t
ether was observed; (b) The bulky BuOH and the electron poor
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CF3CH2OH were tested and did not yield the desired products.
(17) Transmetallation of aryl trimethylsilanes to oxidatively generated
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(18) As highlighted by a referee, we cannot rule out oxygen attack to the
Au(III)-coordinated olefin happening prior to transmetallation in a
catalytic scenario. Furthermore, we note that the complex mixture of
reagents offers many variations on the scheme we propose, such as
the possible involvement of a Brønsted acid in facilitating some of
the transformations shown.
(5) (a) Saini, V.; Sigman, M. S. J. Am. Chem. Soc. 2012, 134, 11372; (b)
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(6) For 1,2-carbodifunctionalization of ethylene via metal-catalyzed
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(20) Fuchita, Y.; Utsunomiya, Y.; Yasutake, M. J. Chem. Soc., Dalton
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In the absence of this additive much slower conversion was observed
but quantitative formation of 2b still occurred after 2 weeks at 50 oC.
t
(21) The commonly used Bu3PAuCl and Cy3PAuCl were also tested as
t
precatalysts under the same conditions. Bu3PAuCl was essentially
inactive whereas Cy3PAuCl showed an activity profile almost iden-
tical to that of (4-CF3C6H4)3PAuCl (see Figure 1 in SI).
(22) Details are given in the SI.
(7) Examples of non-catalytic ethylene 1,2-difunctionalization: (a) Har-
mon, J.; Hanford, W. E.; Joyce, R. M. J. Am. Chem. Soc. 1948, 70,
2529; (b) Owen, G. R.; Reese, C. B. J. Chem. Soc. C 1970, 2401.
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