Addition of arylstannanes to alkynes giving: Ortho -alkenylarylstannanes catalysed cooperatively by a rhodium complex and zinc chloride

Article abstract of DOI:10.1039/c8sc02459f

The reaction of arylstannanes ArSnR₃ with unfunctionalised alkynes was found to proceed in the presence of a rhodium catalyst and a catalytic amount of zinc chloride to give ortho-alkenylarylstannanes with high selectivity in high yields. The c

Full text of DOI:10.1039/c8sc02459f

View Article Online
View Journal
Chemical
Science
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: J. Ming, Q. Shi
and T. Hayashi, Chem. Sci., 2018, DOI: 10.1039/C8SC02459F.
This is an Accepted Manuscript, which has been through the
Volume
7 Number 1 January 2016 Pages 1–812
Royal Society of Chemistry peer review process and has been
accepted for publication.
Chemical
Science
Accepted Manuscripts are published online shortly after
www.rsc.org/chemicalscience
acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.
You can find more information about Accepted Manuscripts in the
author guidelines.
Please note that technical editing may introduce minor changes
to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the ethical guidelines, outlined
in our author and reviewer resource centre, still apply. In no
event shall the Royal Society of Chemistry be held responsible
for any errors or omissions in this Accepted Manuscript or any
consequences arising from the use of any information it contains.
ISSN 2041-6539
EDGE ARTICLE
Francesco Ricci et al.
Electronic control of DNA-based nanoswitches and nanodevices
rsc.li/chemical-science

Please do not adjust margins
Chemical Science
Page 1 of 6
View Article Online
DOI: 10.1039/C8SC02459F
Chemical Science
EDGE ARTICLE
Addition of arylstannanes to alkynes giving ortho-
alkenylarylstannanes catalysed cooperatively by a rhodium
complex and zinc chloride
Received 00th January 20xx,
Accepted 00th January 20xx
Jialin Ming,a Qi Shia and Tamio Hayashia*
DOI: 10.1039/x0xx00000x
www.rsc.org/
Abstract: The reaction of arylstannanes ArSnR3 with be catalysed by transition metals such as Pd and Ni,7,8 but the
unfunctionalised alkynes was found to proceed in the presence of addition of arylstannanes has not been reported, to the best of
a rhodium catalyst and a catalytic amount of zinc chloride to give our knowledge (Scheme 1b). This type of arylmetalation
ortho-alkenylarylstannanes with high selectivity in high yields. The reaction that is accompanied by the 1,4-migration of the metal
catalytic cycle is very unique, consisting of three transmetalation has been reported by Yoshikai for arylzincation catalysed by a
steps, from Sn to Rh, Rh to Zn, and Zn to Sn, in addition to cobalt complex (Scheme 1c).9
arylrhodation of alkyne followed by 1,4-migration of Rh from 2-
arylalkenyl carbon to ortho-alkenylaryl carbon.
(a) Rhodium-catalyzed migratory arylstannylation of alkynes (This Work)
R
SnR3
R
[Rh] (catalyst)
X
+ R
R
R
Introduction
X
ZnCl2 (catalyst)
SnR3
Organostannanes are organometallic reagents widely used for
organic synthesis.1 They are easy to handle because of their
inertness towards oxygen and moisture, while the
organostannanes are reactive with various electrophiles in the
presence of appropriate activators. A typical example is the
palladium-catalysed cross-coupling reaction (Stille coupling).2
The organostannanes have been most commonly prepared by
the reaction of highly reactive organometals (RLi, RMgX) with
tin electrophiles, and considerable attention has been paid to
the development of their new synthetic methods. Palladium-
or nickel-catalysed stannylation of organic electrophiles with
distannanes is one of the examples.3 Here we report our
findings that migratory arylstannylation of unfunctionalised
alkynes is catalysed by Rh complexes in the presence of a
catalytic amount of ZnCl2 to give high yields of ortho-
alkenylarylstannanes with high selectivity. The reaction is
proposed to proceed through 1,4-migration of Rh from alkenyl
carbon to aryl carbon4-6 (Scheme 1a). Carbostannylation of
alkynes with allyl- and alkynylstannanes has been reported to
R
R
R
1,4-Rh migration
X
X
[Rh]
[Rh]
(b) Catalytic carbostannylation of alkynes
Ni, Pd, Ag, Zr
(catalyst)
R1
R2
SnR3
R1
R1, R2 = H, aryl, alkyl, COOR
R3 = allyl, alkynyl (reported): R3 = aryl (not reported)
R2
R3 SnR3
+
R3
(c) Cobalt-catalyzed migratory arylzincation of alkynes (Yoshikai)
R
R
E
ZnCl
CoCl2(Xantphos)
(5 mol%)
R
R
E+
+
ZnCl
R
R
Scheme 1 Arylstannylation of alkynes and 1,4-migration.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
Please do not adjust margins

Please do not adjust margins
Chemical Science
Page 2 of 6
View Article Online
DOI: 10.1039/C8SC02459F
Edge Article
Chemical Science
Table 1 Rhodium-catalysed phenylstannylation of 4-octyne (2a) with PhSnBu3 (1a)a
Table 2 Rhodium-catalysed arylstannylation of 4-octyne (2a) with ArSnR3 1a
Pr
Pr
Pr
SnBu3
Rh/L (5 mol%)
SnR3
[RhCl(coe)2]2 (5.0 mol% of Rh)
binap (or segphos) (5.5 mol%)
Pr
Pr
Pr
X
X
1
SnBu3
additive
dioxane
ZnCl2 (1.0 eq)
SnBu3
1a (0.40 mmol)
+
SnR3
dioxane, 130 °C, 16 h
3
3aa
4aa
Pr
Pr
+
2a
Pr
Pr
O
2a (0.20 mmol)
Entry
ArSnR3 1
L on Rhb
yield (%)c of 3
O
O
PPh2
PPh2
PPh2
PPh2
PPh2
PPh2
1
2
PhSnBu3 (1a)
binap
binapd
binap
85 (3aa)
77 (3ba)
89 (3ca)
78 (3da)
87 (3ea)
91 (3fa)
83 (3ga)
83 (3ha)
65 (3ia)
77 (3ja)
73 (3ka)
84 (3ka)
47 (3la)
78 (3la)
51 (3ma)
67 (3ma)
61 (3na)
82 (3na)
69 (3oa)
77 (3pa)e
84 (3qa)e
67 (3ra)e
83 (3sa)e
<3 (3ta)
PhSnMe3 (1b)
PhSnPr3 (1c)
O
3
binap
segphos
biphep
4
PhSnOct3 (1d)
binap
Entry
Rh catalystb
(5 mol%)
Additive (equiv to 2a)
Yield (%)c of
5
4-MeC6H4SnBu3 (1e)
4-PhC6H4SnBu3 (1f)
binap
3aa
6
binap
1
2
Rh/binap
ZnCl2 (1.0)
ZnCl2 (2.0)
ZnCl2 (0.50)
ZnCl2 (0.25)
ZnCl2 (0.10)
—
85
7
4-Me3SiC6H4SnBu3 (1g)
4-CF3OC6H4SnBu3 (1h)
4-MeOC6H4SnBu3 (1i)
4-FC6H4SnBu3 (1j)
binap
Rh/binap
Rh/binap
Rh/binap
Rh/binap
Rh/binap
Rh/binap
Rh/binap
Rh/binap
Rh/binap
Rh/segphos
Rh/biphep
Rh/dppf
89
73
71
27
0
8
binap
3
9
binapd
4
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
binap
5
4-ClC6H4SnBu3 (1k)
binap
6
7d
ZnCl2 (1.0)
ZnBr2 (1.0)
ZnI2 (1.0)
75
43
18
<3
73
71
16
0
4-ClC6H4SnBu3 (1k)
segphos
binap
4-BrC6H4SnBu3 (1l)
8
4-BrC6H4SnBu3 (1l)
segphos
binap
9
4-NCC6H4SnBu3 (1m)
4-NCC6H4SnBu3 (1m)
4-MeOOCC6H4SnBu3 (1n)
4-MeOOCC6H4SnBu3 (1n)
4-CF3C6H4SnBu3 (1o)
3-MeC6H4SnBu3 (1p)
3-Me3SiC6H4SnBu3 (1q)
3-CF3C6H4SnBu3 (1r)
2-naphthylSnBu3 (1s)
2-MeC6H4SnBu3 (1t)
10
11
12
13
14
15
16
17
18
19
20
CuCl (1.0)
ZnCl2 (1.0)
ZnCl2 (1.0)
ZnCl2 (1.0)
ZnCl2 (1.0)
ZnCl2 (1.0)
ZnCl2 (1.0)
ZnCl2 (1.0)
ZnCl2 (1.0)
ZnCl2 (1.0)
ZnCl2 (1.0)
segphos
binap
segphos
segphos
binap
Rh/dppe
Rh/dppp
0
binap
Rh/xantphos
0
e
binap
Rh/PPh3
<3
0
Rh/codf
Ir/binapg
binap
binap
0
Co/xantphosh
7
a
Reaction conditions: 4-Octyne (2a) (0.20 mmol), ArSnR3 1 (0.40 mmol), ZnCl2
(0.20 mmol) and Rh catalyst (5 mol% of Rh) in dioxane (1.0 mL) at 130 °C (bath
a
Reaction conditions: 4-Octyne (2a) (0.20 mmol), PhSnBu3 (1a) (0.40 mmol)
b
temp) for 16 h. Rh catalyst (5 mol% of Rh) was generated in situ from
and ZnCl2 (0.20 mmol) in dioxane (1.0 mL) at 130 °C (bath temp) for 16 h. b Rh
[RhCl(coe)2]2 (10 μmol of Rh) and binap or segphos (11 μmol). c Isolated yield. d
catalyst (5 mol% of Rh) was generated in situ from [RhCl(coe)2]2 (10 μmol of
In THF at 90 °C. e Regioselective 1,4-shift giving the products 3 shown below.
c
d
e
Rh) and bisphosphine (11 μmol). Isolated yield. At 100 °C. RhCl(PPh3)3 (10
f
g
μmol). [RhCl(cod)]2 (10 μmol of Rh). [IrCl(coe)2]2 (10 μmol of Ir) + binap (11
μmol). h CoCl2(xantphos) (10 μmol).
Pr
Pr
R
Pr
Pr
SnBu3
SnBu3
R = Me (3pa), Me3Si (3qa), CF3 (3ra)
3sa
Results and discussion
The results obtained for the reaction of 4-octyne (2a) with
PhSnBu3 1a, 2.0 equiv to 2a) under various conditions are
(
summarised in Table 1. The migratory arylstannylation was
found to proceed in the presence of ZnCl2 (1.0 equiv to 2a) and
a rhodium catalyst generated from [RhCl(coe)2]2 (5.0 mol % of
2 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Please do not adjust margins
Chemical Science
Page 3 of 6
View Article Online
DOI: 10.1039/C8SC02459F
Chemical Science
Edge Article
Rh) and binap10 (5.5 mol%) in dioxane at 130 °C for 16 h to give and 14). In the arylstannylation with meta-substituted aryltin
85% yield of 4-(2-stannylphenyl)-4-octene (3aa) with perfect E reagents, perfect regioselectivity at the 1,4-migration was
geometry11 (entry 1). The direct arylstannylation product 4aa observed. Thus, the reaction of those substituted with Me
was not formed in a detectable amount under these reaction
(
1p), Me3Si (1q) and CF3
(
1r) gave the corresponding 2,4-
conditions. The yield of 3aa was dependent on the amount of disubstituted aryltins 3pa
–
3ra, which are the less hindered
ZnCl2 to some extent. With 2.0 equiv of ZnCl2, the yield was isomers, exclusively (entries 20–22). The regioselectivity was
slightly increased (89%) (entry 2). The yields were lower with also high for the reaction of 2-naphthyltin 1s, where the 1,4-
less amount of ZnCl2, being 73%, 71% and 27%, with 0.50, 0.25 migration took place to the less hindered 3-position selectively
and 0.10 equiv of ZnCl2, respectively (entries 3–5). It is noted (entry 23). Unfortunately, the migratory arylstannylation did
that ZnCl2 is working as a catalyst though a substoichiometric not take place for ortho-substituted tin reagent 1t under the
amount is necessary for a high yield of 3aa. The presence of present conditions (entry 24).
ZnCl2 is essential for the present arylstannylation, 3aa being
Table 3 Rhodium-catalysed arylstannylation of alkynes 2 with PhSnBu3 (1a)a
not formed at all in its absence (entry 6). At lower reaction
temperature (100 °C), the yield of 3aa was lower by 10% (entry
7). Other zinc halides, ZnBr2 and ZnI2 were less catalytically
active than ZnCl2 (entries 8 and 9). It is difficult to find a
substitute of ZnCl2 from other metal salts. CuCl12 gave a trace
amount of 3aa (entry 10). The binap ligand on Rh can be
replaced by segphos or biphep, both of which are analogous to
binap in that their backbones connecting two phosphino
groups are biaryls. The yields with segphos13 and biphep were
slightly lower (73% and 71%, respectively) than that with binap
for the reaction of PhSnBu3 (1a) (entries 11 and 12), but for the
reactions of some other arylstannanes, the yields of the
arylstannylation products are higher with segphos ligand (see
Table 2). The catalytic activity of other phosphine–Rh
complexes were much lower. While dppf ligand gave a low
yield (16%) of 3aa (entry 13), the reaction did not take place
with dppe, dppp, xantphos or PPh3 (entries 14–17). Rh
complex with cyclooctadiene (cod) ligand or Ir/binap complex
did not catalyse the reaction either (entries 18 and 19). The
cobalt complex, CoCl2(xantphos), which has been reported to
be an effective catalyst for the migratory arylzincation,9 is not
a catalyst of choice for the present arylstannylation, yielding
only 7% of 3aa (entry 20).
R1
SnBu3
[RhCl(coe)2]2 (5.0 mol% of Rh)
binap (5.5 mol%)
R2
1a
ZnCl2 (1.0 eq)
+
SnBu3
dioxane, 130 °C, 16 h
R1
R2
3
2b–2l
c-Hex
Me
Alk
3aa (Alk = n-C3H7): 85% yield
3ab (Alk = n-C4H9): 84% yield
3ac (Alk = n-C7H15): 83% yield
Alk
SnBu3
Ar
SnBu3
3ad: 84% yield
(regio: 1.2/1)
3ae (Ar = Ph): 72% yield
Ar
Ar
3af (Ar = 4-MeOC6H4): 78% yield
3ag (Ar = 4-FC6H4): 74% yield
SnBu3
Alk
3ah (Alk = C2H5, Ar = Ph): 73% yield (regio: 9/1)
3ai (Alk = C2H5, Ar = 4-Me3SiC6H4): 77% yield (regio: 10/1)
3aj (Alk = C2H5, Ar = 3,4,5-MeO3C6H2): 76% yield (regio: 17/1)
3ak (Alk = n-C3H7, Ar = Ph): 71% yield (regio: 8/1)
3al (Alk = n-C4H9, Ar = Ph): 73% yield (regio: 7/1)
SnBu3
a Reaction conditions: Alkyne 2 (0.20 mmol), PhSnBu3 1a (0.40 mmol), ZnCl2 (0.20
mmol) and Rh catalyst (5 mol% of Rh), generated in situ from [RhCl(coe)2]2 (10
μmol of Rh) and binap (11 μmol), in dioxane (1.0 mL) at 130 °C (bath temp) for 16
h. The structures of main regioisomers are shown for the products from
unsymmetrically substituted alkynes.
The
reaction
conditions
optimised
for
the
phenylstannylation with PhSnBu3 (1a), that is, with Rh/binap (5
mol%) and ZnCl2 (1.0 equiv) at 130 °C (entry 1 in Table 1), were
successfully applied to the reaction of several other aryltin
reagents ArSnR3 with 4-octyne (2a) (Table 2). The phenyltin
reagents PhSnR3, where R is methyl (1b), propyl (1c) and octyl
The results obtained for the reaction of PhSnBu3 (1a) with
several unfunctionalised alkynes substituted with alkyl and aryl
groups are summarised in Table 3. The migratory
arylstannylation proceeded well for longer-chained
dialkylacetylenes, 5-decyne (2b) and 8-hexadecyne (2c), to give
(
1d), all gave the corresponding phenylstannylation products
3ba–3da in high yields (entries 2–4). The yields are generally
high yields of the corresponding products, 3ab and 3ac
,
high for para-substituted aryltin reagents, those substituted
with Me, Ph, Me3Si and CF3O groups giving the corresponding
products in 83–91% yields (entries 5–8). The lower yield (65%)
for MeO-substituted one 1i is mainly due to the instability of
the product 3ia under the reaction conditions (entry 9). For
the reaction of aryltin reagents substituted with electron-
respectively. In the reaction of unsymmetrically substituted
dialkylacetylene 2d, the regioselectivity at the addition to
alkyne was low, resulting in the formation of a mixture of 3ad
and its regioisomer in a ratio of 1.2/1.0. Diarylacetylenes also
underwent the migratory arylstannylation, although the yields
are generally lower than those for dialkylacetylenes.14 The
withdrawing groups at para-position, Cl (1k), Br (1l), CN (1m
)
reaction of alkyl(aryl)alkynes 2h–2l, proceeded with high
and COOMe (1n), the Rh/binap catalyst was not very effective
resulting in lower yields of the corresponding arylstannylation
products. The use of Rh/segphos as a catalyst instead of
Rh/binap improved the reaction for these aryltin reagents
(entries 11–18).A typical example is the reaction of 4-
BrC6H4SnBu3, where the yields of the product 3la are 47% and
78% with binap and segphos ligands, respectively (entries 13
regioselectivity for the bond formation between phenyl group
of phenyltin 1a and alkyl-substituted alkyne carbon. This
selectivity is as expected from the reported regiochemistry at
carbometalation of alkyl(aryl)alkynes.15
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
Please do not adjust margins

Please do not adjust margins
Chemical Science
Page 4 of 6
View Article Online
DOI: 10.1039/C8SC02459F
Edge Article
Chemical Science
Ph–Rh complex, RhPh(PPh3)(binap) (
5
),18 with ClSnBu3 (2.0 eq)
SnR3
R
1
in the presence of ZnCl2 (1.2 eq) in dioxane at 130 °C gave 93%
yield of PhSnBu3 (1a), while the yield of 1a is very low (12%) in
the absence of ZnCl2 under otherwise the same conditions
(Scheme 3a). These reactions are related to the last
R
R
R
transmetalation
[Rh]
Cl [Rh]
ZnCl
A
E
B
2
transmetalation
ClSnR3
transmetalation step producing
in the catalytic cycle. The results show that the direct
transmetalation between intermediate and ClSnR3 is slow
3 from Ar–Rh intermediate D
arylrhodation
R
R
R
transmetalation
R
R
D
[Rh]
R
SnR3
and that ZnCl2 greatly accelerates the transmetalation. The fast
transmetalation in the presence of ZnCl2 is probably because
of a lower energy caused by the double transmetalations from
ZnCl2
C
3
[Rh]
1,4-Rh shift
D
Rh to Zn and from Zn to Sn by way of arylzinc species E.
Scheme 2 A catalytic cycle proposed for migratory arylstannylation of alkynes catalysed
by Rh complex and ZnCl2.
Rhodium-catalysed 1,4-migration of Sn from alkenylstannane
4ae to arylstannane 3ae was observed in the presence of
ZnCl2, albeit in a low yield (16%).19 The 1,4-migration of Sn did
not take place in the absence of ZnCl2 (Scheme 3b). The
The reaction pathway of the present migratory
arylstannylation of alkynes, which is catalysed cooperatively by
Rh complex and ZnCl2, is proposed as shown in Scheme 2.
Thus, the transmetalation of phenyl group from Sn to Rh takes
catalytic cycle involving the 1,4-Rh shift from intermediates
to is supported by these results. The deuterium-labeling
study using C6D5SnBu3 1a-d5) (Scheme 3c), where the
C
D
(
place at the reaction of PhSnR3
generate Ph–Rh intermediate
to be involved at the final step leading to the stannylation
product . The syn-addition of Ph–Rh to alkyne generates
2-arylalkenyl–Rh and 1,4-migration of Rh from alkenyl to
phenyl4,5 gives ortho-alkenylphenyl–Rh intermediate
, which
has been reported to be thermodynamically more stable than
C 5e
Transmetalation between the ortho-alkenylpheny–Rh
and ZnCl2 takes place to give arylzinc chloride and the Cl–Rh
species . Finally, the reaction of arylzinc chloride with
ClSnR3, which was formed at the transmetalation between
PhSnR3 and Cl–Rh , leads to ortho-alkenylphenystannane
with regenerating ZnCl2. Direct transmetalation between the
Ar–Rh intermediate and PhSnR3 giving Ph–Rh and the
product is less likely because a catalytic amount of ZnCl2 is
1
with a Cl–Rh species
A to
B
and ClSnR3,16 the latter being
deuterium is incorporated at olefinic carbon in 3aa-d5, further
supports this catalytic cycle involving the 1,4-Rh shift. The
present Rh/ZnCl2 cocatalyst system is also applicable to the
addition of PhZnCl (6a) to 4-octyne (2a) generating ortho-
3
B
2
C
alkenylphenylzinc spiecies 7 20
ClSnBu3 gave 78% yield of the tin compound 3aa (Scheme 3d).
,
the reaction of which with
D
.
D
Pr
Pr
E
E
Pr
Pr
A
E
(a), (b), or (c)
17
E = D (8): 98%
I (9): 87%
F (10): 69%
SnBu3
(d)
1
A
3,
3aa
(e)
Pr
D
1
B
Pr
Pr
3
Pr
essential for the present arylstannylation to take place (see
entries 1–6 in Table 1).
O
11: 83%
12: 87%
COOMe
ClSnBu3 (2.0 eq)
P
(a) (CF3CO)2O, D2O. (b) I2, CH2Cl2. (c) selectfluor, AgOTf, acetone. (d) 4-IC6H4COOMe,
PdCl2(PPh3)2 (10 mol%), CuI, DMF. (e) 2-cyclohexenone, [RhCl(cod)]2 (5 mol% Rh),
KOH, dioxane/H2O.
(a)
Rh
93% with ZnCl2
with or without ZnCl2 (1.2 eq)
dioxane, 130 °C, 30 min
Ph3P
P
SnBu3
Ph
12% without ZnCl2
5
1a
P
P
= binap
Scheme 4 Transformation of ortho-alkenylarylstannane 3aa.
Ph
[RhCl(coe)2]2 (15 mol% of Rh)
binap (16 mol%)
Ph
Ph
16% with ZnCl2
The synthetic utility of arylstannanes has been well
established.1 According to the reported procedures,21–23
(b)
(c)
0% without ZnCl2
SnBu3
with or without ZnCl2 (3.0 eq)
dioxane, 130 °C, 16 h
SnBu3
4ae
3ae
tributylstannyl group in 3aa was converted into deuterio (
8),
D
D
D
Pr
iodo
(9) and fluoro (10) successfully (Scheme 4). The
[RhCl(coe)2]2 (5.0 mol% of Rh)
binap (5.5 mol%)
D
SnBu3
D
Pr
palladium-catalysed cross-coupling with an aryl iodide2 and the
rhodium-catalysed conjugate addition to 2-cyclohexenone16
>90% D
+
Pr
Pr
D
ZnCl2 (1.0 eq)
D
D
D
SnBu3
dioxane, 130 °C, 16 h
D
gave high yields of the corresponding products, 11 and 12
,
2a
1a-d5
3aa-d5: 87%
respectively, as expected.
ZnCl
Pr
Pr
[RhCl(coe)2]2 (5 mol% of Rh)
binap (5.5 mol%)
Pr
Pr
ClSnBu3
6a
(d)
+
ZnCl2 (1.0 eq)
ZnCl
SnBu3
3aa: 78%
Pr
Pr
dioxane, 130 °C, 5 h
Conclusions
7
2a
To summarise, migratory arylstannylation was found to take
place in the reaction of arylstannanes ArSnR3 with
unfunctionalised alkynes in the presence of a bisphosphine–
rhodium catalyst and a catalytic amount of zinc chloride to
Scheme 3 Reactions to support the catalytic cycle.
The reactions shown in Scheme
3 gave us further
information on the catalytic cycle. Stoichiometric reactions of
4 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Please do not adjust margins
Chemical Science
Page 5 of 6
View Article Online
DOI: 10.1039/C8SC02459F
Chemical Science
Edge Article
Soc., 2000, 122, 10464; (b) T. Matsuda, M. Shigeno and M.
Murakami, J. Am. Chem. Soc., 2007, 129, 12086; (c) J.
Panteleev, F. Menard and M. Lautens, Adv. Synth. Catal.,
2008, 350, 2893; (d) T. Seiser, O. A. Roth and N. Cramer,
Angew. Chem. Int. Ed., 2009, 48, 6320; (e) M. Shigeno, T.
produce ortho-alkenylarylstannanes in high yields. A catalytic
cycle involving three transmetalation steps is proposed. That
is, transmetalation of aryl groups from Sn to Rh, Rh to Zn, and
Zn to Sn.
Yamamoto and M. Murakami, Chem. –Eur. J., 2009, 15
12929; (f) T. Seiser and N. Cramer, Chem. –Eur. J., 2010, 16
,
,
3383; (g) T. Seiser and N. Cramer, Angew. Chem. Int. Ed.,
2010, 49, 10163; (h) T. Matsuda, Y. Suda and A. Takahashi,
Chem. Commun., 2012, 48, 2988; (i) H. Yu, C. Wang, Y. Yang
and Z.-M. Dang, Chem. –Eur. J., 2014, 20, 3839; (j) R.
Conflicts of interest
There are no conflicts to declare.
Shintani, R. Iino and K. Nozaki, J. Am. Chem. Soc., 2014, 136
,
7849; (k) H. B. Hepburn and H. W. Lam, Angew. Chem. Int.
Ed., 2014, 53, 11605; (l) T. Sawano, M. Hashizume, S.
Acknowledgements
This work was supported by funding from Nanyang
Technological University and the Singapore Ministry of
Education (AcRF MOE 2016-T1-001-247 and 2017-T2-1-064).
Nishimoto, K. Ou and T. Nishimura, Org. Lett., 2015, 17
2630; (m) J. Ming and T. Hayashi, Org. Lett., 2016, 18, 6452.
,
7
For reviews on carbostannylation of C–C multiple bonds: (a)
H. Yoshida, Synthesis, 2016, 48, 2540; (b) E. Shirakawa,
Carbostannylation of Carbon–Carbon Unsaturated Bonds, In
Tin Chemistry: Fundamentals, Frontiers, and Applications, M.
Gielen, A. G. Davies, K. H. Pannell and E. R. Tiekink, John
Notes and references
Wiley
Shirakawa and T. Hiyama, Bull. Chem. Soc. Jpn., 2002, 75
1435. (d) E. Shirakawa and T. Hiyama, J. Organomet. Chem.,
2002, 653, 114.
Examples of carbostannylation of alkynes: (a) M. Shimizu, G.
Jiang, M. Murai, Y. Takeda, Y. Nakao, T. Hiyama and E.
Shirakawa, Chem. Lett., 2005, 34, 1700; (b) E. Shirakawa, Y.
Yamamoto, Y. Nakao, S. Oda, T. Tsuchimoto and T. Hiyama,
Angew. Chem. Int. Ed., 2004, 43, 3448; (c) E. Shirakawa, H.
& Sons, Chichester, 2008, pp. 640–652; (c) E.
,
1
(a) M. Gielen, A. G. Davies, K. H. Pannell and E. Tiekink, Tin
chemistry: fundamentals, frontiers, and applications, Wiley,
2008; (b) A. G. Davies, In Organotin Chemistry, 2nd Edn.,
Wiley-VCH, Weinheim, 2004, p. 140; (c) M. Pereyre, J.-P.
Quintard and A. Rahm, Tin in Organic Synthesis,
Butterworths & Co., 1987.
8
9
2
(a) C. Cordovilla, C. Bartolomé, J. M. Martínez-Ilarduya and P.
Espinet, ACS Catal., 2015, 5, 3040; (b) A. de Meijere, S. Bräse
and M. Oestreich, Metal-Catalyzed Cross-Coupling Reactions
and More, Wiley-VCH, Weinheim, 2014; (c) M. M. Heravi, E.
Hashemi and F. Azimian, Tetrahedron, 2014, 70, 7; (d) B.
Carsten, F. He, H. J. Son, T. Xu and L. Yu, Chem. Rev., 2011,
111, 1493; (e) V. Farina, V. Krishnamurthy and W. J. Scott,
The Stille Reaction, Wiley, New York, 2004; (f) P. Espinet and
A. M. Echavarren, Angew. Chem. Int. Ed., 2004, 43, 4704.
(a) D. Azarian, S. S. Dua, C. Eaborn and D. R. M. Walton, J.
Organomet. Chem., 1976, 117, C55; (b) A. N. Kashin, I. G.
Bumagina, N. A. Bumagin, V. N. Bakunin and I. P. Beletskaya,
J. Org. Chem. USSR., 1981, 17, 789; (c) M. Kosugi, T. Ohya
and T. Migita, Bull. Chem. Soc. Jpn., 1983, 56, 3855; (d) W. D.
Wulff, G. A. Peterson, W. E. Bauta, K.-S. Chan, K. L. Faron, S.
R. Gilbertson, R. W. Kaesler, D. C. Yang and C. K. Murray, J.
Org. Chem., 1986, 51, 277; (e) E. B. Corcoran, A. B. Williams
and R. N. Hanson, Org. Lett., 2012, 14, 4630; (f) J. E. Pickett,
A. Váradi, T. C. Palmer, S. G. Grinnell, J. M. Schrock, G. W.
Pasternak, R. R. Karimov and S. Majumdar, Bioorg. Med.
Chem. Lett., 2015, 25, 1761; (g) Y. Gu and R. Martín, Angew.
Chem. Int. Ed., 2017, 56, 3187; (h) H. Yue, C. Zhu and M.
Rueping, Org. Lett., 2018, 20, 385.
For reviews dealing with 1,4-metal shift, see: (a) M. F.
Croisant, R. van Hoveln and J. M. Schomaker, Eur. J. Org.
Chem., 2015, 5897; (b) F. Shi and R. C. Larock, Top. Curr.
Chem., 2010, 292, 123; (c) T. Miura and M. Murakami, Chem.
Commun., 2007, 217; (d) S. Ma and Z. Gu, Angew. Chem. Int.
Ed., 2005, 44, 7512.
For 1,4-Rh shift from alkenyl to aryl, see: (a) T. Hayashi, K.
Inoue, N. Taniguchi and M. Ogasawara, J. Am. Chem. Soc.,
2001, 123, 9918; (b) T. Miura, T. Sasaki, H. Nakazawa and M.
Murakami, J. Am. Chem. Soc., 2005, 127, 1390; (c) R.
Shintani, K. Takatsu and T. Hayashi, Angew. Chem. Int. Ed.,
2007, 46, 3735; (d) R. Shintani, S. Isobe, M. Takeda and T.
Hayashi, Angew. Chem. Int. Ed., 2010, 49, 3795; (e) K. Sasaki,
T. Nishimura, R. Shintani, E. A. B. Kantchev and T. Hayashi,
Yoshida, Y. Nakao and T. Hiyama, J. Am. Chem. Soc., 1999
121, 4290.
,
(a) B.-H. Tan, J. Dong and N. Yoshikai, Angew. Chem. Int. Ed.,
2012, 51, 9610; See also: (b) B.-H. Tan and N. Yoshikai, Org.
Lett., 2014, 16, 3392; (c) J. Wu and N. Yoshikai, Angew.
Chem. Int. Ed., 2016, 55, 336; (d) J. Yan and N. Yoshikai, Org.
Chem. Front., 2017, 4, 1972.
3
10 H. Takaya, K. Mashima, K. Koyano, M. Yagi, H. Kumobayashi,
T. Taketomi, S. Akutagawa and R. Noyori, J. Org. Chem.,
1986, 51, 629.
11 The E geometry was confirmed by nOe studies of 3aa and
3na and X-ray crystal structure analysis of 3ag. See
Supporting Information.
12 CuBr has been used as
a cocatalyst in Fe-catalysed
arylmagnesiation of alkynes: E. Shirakawa, T. Yamagami, T.
Kimura, S. Yamaguchi and T. Hayashi, J. Am. Chem. Soc.,
2005, 127, 17164.
13 T. Saito, T. Yokozawa, T. Ishizaki, T. Moroi, N. Sayo, T. Miura
and H. Kumobayashi, Adv. Synth. Catal., 2001, 343, 264.
14 The lower yields are due mainly to the formation of higher
molecular weight compounds.
15 For a pertinent review on catalytic carbometallation of
alkynes: K. Murakami and H. Yorimitsu, Beilstein J. Org.
Chem., 2013, 9, 278.
16 The transmetalation from Sn to Rh has been reported for the
conjugate addition of aryl- and alkenylstannanes to α,β-
unsaturated carbonyl compounds: (a) S. Oi, M. Moro, S. Ono
and Y. Inoue, Chem. Lett., 1998, 83; (b) S. Venkatraman, Y.
Meng and C.-J. Li, Tetrahedron Lett., 2001, 42, 4459; (c) S. Oi,
M. Moro, H. Ito, Y. Honma, S. Miyano and Y. Inoue,
Tetrahedron, 2002, 58, 91; (d) S. J. Mahoney, A. M. Dumas
and E. Fillion, Org. Lett., 2009, 11, 5346.
4
5
17 The reaction of ClSnR3 with ArZnX giving ArSnR3 has been
reported: As an early example, X. Zhu, B. E. Blough and F. I.
Carroll, Tetrahedron Lett., 2000, 41, 9219.
18 T. Hayashi, M. Takahashi, Y. Takaya and M. Ogasawara, J.
Am. Chem. Soc., 2002, 124, 5052. See also, G. E. Rudebusch,
Chem. Sci., 2012, 3, 1278; (f) K. Sasaki and T. Hayashi,
Tetrahedron: Asymmetry, 2012, 23, 373.
For examples of other types of 1,4-Rh shift, see: (a) K.
Oguma, M. Miura, T. Satoh and M. Nomura, J. Am. Chem.
6
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
Please do not adjust margins

Please do not adjust margins
Chemical Science
Page 6 of 6
View Article Online
DOI: 10.1039/C8SC02459F
Edge Article
Chemical Science
L. N. Zakharov and S.-Y. Liu, Angew. Chem. Int. Ed., 2013, 52
9316.
,
19 The low yield is mainly because of low conversion of the
alkenylstannane 4ae
.
20 The reaction of arylzinc reagents with unfunctionalized
alkynes cocatalysed by a Rh complex and ZnCl2 will be
reported in detail in a separate paper.
21 D. E. Seitz, R. A. Milius and H. El-Wakil, Synth. Commun.,
1981, 11, 281.
22 D. E. Seitz, G. L. Tonnesen, S. Hellman, R. N. Hanson and S. J.
Adelstein, J. Organomet. Chem., 1980, 186, C33.
23 T. Furuya, A. E. Strom and T. Ritter, J. Am. Chem. Soc., 2009,
131, 1662.
6 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins