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S. Webster et al.
Letter
Synlett
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RS
H
RS
H
[M]
RS
H
I
RL
O
H
RL
O
R
RL
XR
E-selectivity
R
–[M]
X
X
H2O
[M]
II
3
S = small
L = large
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Scheme 3
In conclusion, indium(III) chloride can be used as a
cheaper alternative catalyst to gold(I) in dehydrative reac-
tions with allylic alcohols. Furthermore, among the sub-
strates investigated, there was often an improvement in
yield for indium(III) chloride catalysis in comparison with
gold(I) catalysis; this improvement ranged from moderate
to significant. In particular, indium(III) chloride outper-
formed gold(I) when chemoselectivity was an issue. For ex-
ample, gold(I) gave a complex mixture of products from
substrates containing pendent alkene or alkyne groups (for
example, 1c and 2g), whereas indium(III) chloride success-
fully gave the desired products. Another situation in which
indium(III) outperforms gold(I) as a catalyst is when the
substrate contains proximal heteroatoms, as in the case of
the nucleophile 2d. We therefore hope that our studies will
encourage others to consider indium(III) chloride as an al-
ternative catalyst for dehydrative reactions with allylic al-
cohols, especially in situations where pendent C–C π-bonds
are present.
(5) (a) Young, P. C.; Schopf, N. A.; Lee, A.-L. Chem. Commun. 2013,
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(9) For In(III) versus Au(I) studies in hydroarylations, see: Kumar,
A.; Li, Z. H.; Sharma, S. K.; Parmar, V. S.; Van der Eycken, E. V.
Chem. Commun. 2013, 49, 6803.
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Acknowledgment
We thank EPSRC (EP/K00736X/1) and Heriot-Watt University (James
Watt Scholarship, S.W.) for funding. Mass spectrometry data were ac-
quired at the EPSRC UK National Mass Spectrometry Facility at Swan-
sea University.
Supporting Information
Supporting information for this article is available online at
S
u
p
p
o
nrtIo
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f
rmoaitn
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ortiInfogrmoaitn
References and Notes
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(14) S-(3,3-Dicyclohexylprop-2-en-1-yl)
Benzenecarbothioate
(3bc); Typical Procedure
A solution of allylic alcohol 1b (221 mg, 1.0 mmol, 1 equiv) in
CHCl3 (1.0 mL) was added to a vial containing InCl3 (10 mg, 5
mol%), thioacid 2c (130 μL 1.1 mmol, 1.1 equiv), and CHCl3 (8
mL). The solution was washed in with a further portion of CHCl3
(1 mL), and the mixture was stirred at 50 °C for 2 h. Purification
by column chromatography [silica gel, hexane–Et2O (7:1)] gave
a colorless oil; yield: 332 mg (97%, 0.969 mmol); Rf = 0.76
(hexane–Et2O, 3:1). IR: 2922, 2849 (C–H), 1660 (C=O), 1596,
© Georg Thieme Verlag Stuttgart · New York — Synlett 2015, 26, 2673–2678