PleaseC dh oe mn oi ct a al dS cj ui es nt cme argins
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Department of Chemistry (T.K.), and Royal Society (UF100592,
UF150675; A.B.C.) for financial support. T.K. acknowledges the
DJEI/DES/SFI/HEA Irish Centre for High-End Computing (ICHEC)
for the provision of computational facilities and support. Laura
Scally, Adrian Deacon and Sean O. Dowd are thanked for
generating preliminary DFT results. High-resolution mass-
spectrometry data were collected using instruments purchased
through support from Advantage West Midlands and the
European Regional Development Fund. Crystallographic data
were collected using an instrument that received funding from
the ERC under the European Union’s Horizon 2020 research and
innovation programme (grant agreement No 637313).
Commun., 2006, 197–199.
DOI: 10.1039/C9SC06153C
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Parallels may be drawn with cycloaddition reactions of
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B. M. Trost and J. T. Masters, Chem. Soc. Rev., 2016, 45, 2212–
0 Formation of 3b by coordination of 2b directly to I and a
2
238.
carbometallation mechanism was also calculated, but the
S. D. Pike, M. R. Crimmin and A. B. Chaplin, Chem. Commun.,
‡
barrier for 1,2-migratory insertion is prohibitively high (ΔG =
2
017, 53, 3615–3633.
-
1
+
28.0 kcal mol , with respect to IV). Details are provided in
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the Supporting Information.
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1 As the homocoupling of 2j proceeds with orthogonal
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2
013, 19, 15304–15314; (b) L. Leroyer, V. Maraval and R.
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(
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-1
ΔΔG = –1.4 kcal mol . Moreover, this step is reversible with
respect to formation of 3b. Details are provided in the
Supporting Information.
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2 (a) T. M. Hood, B. Leforestier, M. R. Gyton and A. B. Chaplin,
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3 This suggestion would infer the annulation rate is independent
of the gem-enyne concentration. From inspection of the time
course data recorded for 4a this does not appear to be the case
for the Ar’ substituted-system, where instead turnover limiting
oxidative coupling would be more consistent with the data. The
1
1
0 (a) R. E. Andrew, L. González-Sebastián and A. B. Chaplin,
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2
2 4
reactivity of macrocyclic 6∙C H with 3a notably provides
experimental evidence the latter step takes place with a fac-
and not mer- coordinated CNC ligand.
1
2
Chakraborty, L. J. W. Shimon, Y. Ben-David and D. Milstein,
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