Catalytic Dehydrogenative Stannylation of C(sp)-H Bonds Involving Cooperative Sn-H Bond Activation of Hydrostannanes

Article abstract of DOI:10.1021/jacs.7b13088

The catalytic generation of a stannylium-ion-like tin electrophile by heterolytic cleavage of the Sn-H bond in hydrostannanes at the Ru-S bond of Ohki-Tatsumi complexes is reported. Reacting these activated hydrostannanes with terminal acetylenes does not lead to hydrostannylation of the C-C triple bond but to dehydrogenative stannylation of the alkyne terminus. The scope of this rare direct C(sp)-H bond stannylation with hydrostannanes is broad, and a mechanism involving a β-tin-stabilized vinyl cation likely having a bridged structure is presented.

Full text of DOI:10.1021/jacs.7b13088

Subscriber access provided by READING UNIV
Communication
Catalytic Dehydrogenative Stannylation of C(sp)-H Bonds
Involving Cooperative Sn-H Bond Activation of Hydrostannanes
Francis Forster, Victoria M. Rendón López, and Martin Oestreich
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.7b13088 • Publication Date (Web): 17 Jan 2018
Downloaded from http://pubs.acs.org on January 17, 2018
Just Accepted
“Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted
online prior to technical editing, formatting for publication and author proofing. The American Chemical
Society provides “Just Accepted” as a free service to the research community to expedite the
dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts
appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been
fully peer reviewed, but should not be considered the official version of record. They are accessible to all
readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered
to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published
in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just
Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor
changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers
and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors
or consequences arising from the use of information contained in these “Just Accepted” manuscripts.
Journal of the American Chemical Society is published by the American Chemical
Society. 1155 Sixteenth Street N.W., Washington, DC 20036
Published by American Chemical Society. Copyright © American Chemical Society.
However, no copyright claim is made to original U.S. Government works, or works
produced by employees of any Commonwealth realm Crown government in the
course of their duties.

Page 1 of 5
Journal of the American Chemical Society
1
2
3
4
5
6
7
8
9
Catalytic Dehydrogenative Stannylation of C(sp)–H Bonds Involving
Cooperative Sn–H Bond Activation of Hydrostannanes
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Francis Forster, Victoria M. Rendón López, and Martin Oestreich*
Institut für Chemie, Technische Universität Berlin, Strasse des 17. Juni 115, 10623 Berlin, Germany
Supporting Information Placeholder
nBu3SnH (2a) to Et3SnH (2b) or Ph3SnH (2c) afforded lower
yield and diminished selectivity (entry 9) or resulted in hy‐
drostannane degradation (entry 10). When using hydrostan‐
nanes 2a and 2b, the corresponding distannanes did form in
trace amounts but cleavage of the Sn–Sn bond by [5]+[A]– did
not occur as verified by independent experiments.—We note
that 2 was used as the limiting reagent for practical reasons;
full consumption of the hydrostannane 2 avoided its remov‐
al.
ABSTRACT: The catalytic generation of a stannylium‐ion‐
like tin electrophile by heterolytic cleavage of the Sn–H bond
in hydrostannes at the Ru–S bond of Ohki–Tatsumi com‐
plexes is reported. Reacting these activated hydrostannanes
with terminal acetylenes does not lead to hydrostannylation
of the C–C triple bond but to dehydrogenative stannylation
of the alkyne terminus. The scope of this rare direct C(sp)–H
bond stannylation with hydrostannanes is broad, and a
mechanism involving a β‐tin‐stabilized vinyl cation having a
bridged structure is presented.
Table 1. Optimization of the Dehydrogenative C(sp)–
Sn Couplinga
One way to achieve cross‐coupling at an sp‐hybridized car‐
bon atom1 is by the Stille reaction.2 The necessary coupling
partner is an alkynyl‐substituted tin compound, and these
are commonly prepared by the reaction of an (earth) alkali
metal acetylide with a tin electrophile such as R3SnCl and
R3SnBr (R = alkyl and aryl).3 Alternatively, tin amides4 and
alkoxides5 engage in direct bond formation with terminal
acetylenes. Recently, the limited scope of these methods was
greatly expanded by Baba and co‐workers who discovered
that ZnBr2 catalyzes the stannylation of terminal alkynes
with nBu3SnOMe.6 We are aware of an unexpected finding by
Mitchell where the use of Me3SnH instead of nBu3SnH in the
planned rhodium‐catalyzed hydrostannylation of the termi‐
nal triple bond of propargyl ethers resulted in unexpected
dehydrogenative C(sp)–Sn coupling.7 Aside from this isolated
report, the formation of vinyl stannanes is the usual outcome
of reactions of alkynes and hydrostannanes.8
entry catalyst
(mol %)
stannane
(R in 2)
t
3a:4a conv.
(h) (%)b
(%)b,c
>99d
>99d
>99d
1
NaOH (10)
nBu (2a)
nBu (2a)
nBu (2a)
nBu (2a)
nBu (2a)
nBu (2a)
nBu (2a)
72
72
72
18
18
18
18
18
24
24
—
—
—
2
3
KOtBu (10)
NaOtBu (10)
4
5
6
7
8
9
10
[5a]+[BArF ]– (1.0)
[5b]+[BArF ]– (1.0)
[5c]+[BArF ]– (1.0)
[5d]+[BArF ]– (1.0)
[5b]+[B(C6F5)4]– (1.0) nBu (2a)
[5b]+[BArF ]– (1.0)
[5b]+[BArF ]– (1.0)
>99:1 32
4
>99:1 >99 (90)
>99:1 80
4
4
96:4
32
4
Inspired by the recent work of Stoltz and Grubbs,9 we tested
alkali metal hydroxides and tert‐butoxides as catalysts in the
C(sp)–H bond stannylation of alkynes 1 with hydrostannanes
2 but that merely led to decomposition of 2 (Table 1, entries
1–3); the same setup had allowed for efficient C(sp)–H bond
silylation. We then turned toward Ohki–Tatsumi complexes
[5]+[A]– as catalysts (Figure 1).10 The Ru–S bond in [5]+[A]–
mediates the cooperative activation of main‐group metal
hydrides,11 and we have been able to develop several dehy‐
drogenative couplings based on this activation mode, partic‐
ularly with hydrosilanes.12 To our delight, any of our typical
>99:1 >99
Et (2b)
Ph (2c)
93:7
—
>99 (66)
90d
4
4
aAll reactions were performed according to the reported
procedure (entries 1–3; Ref. 9) and General Procedure 1 (en‐
tries 4–11; see the Supporting Information for details). bRatios
and conversions were determined by GLC analysis using
tetracosane as an internal standard. cIsolated yield after
d
filtration over Al2O3. Decomposition of the hydrostannane
was observed.
catalysts [5]+[BArF ]– promoted the C(sp)–Sn coupling (1a →
4
3aa; Table 1, entries 4–7). The yield was highest with
[5b]+[BArF ]– (entry 5), and hydrostannylation became a
4
minor pathway with [5d]+[BArF ]– (1a → 4aa; entry 7).
4
[5b]+[B(C6F5)4]–13 with a different counteranion performed
equally well (entry 8). Changing the hydrostannane from
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 2 of 5
1
2
3
4
5
6
7
8
9
13
1m (R = cPent)
[BArF ]–
>99:1
>99:1
>99:1
>99:1
99:1
90 (3ma)
89 (3na)
92 (3oa)
88 (3pa)
66 (3qa)
87 (3ra)
45 (3sa)
84 (3ta)
4
14
15
1n (R = Cy)
[BArF ]–
4
1o (R = nBu)
1p (R = (CH2)3Cl)
1q (R = (CH2)2Br)
1r (R = SiMe3)
1s (R = SiiPr3)
1t
[BArF ]–
4
16
17e
18e
19
20
[BArF ]–
4
[BArF ]–
4
[B(C6F5)4]– >99:1
[BArF ]–
>99:1
>99:1
4
Figure 1. Coordinatively unsaturated Ru–S complexes for
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
cooperative activation of main‐group metal hydrides. ArF
3,5‐bis(trifluoromethyl)phenyl.
=
[BArF ]–
4
aAll reactions were performed according to General Proce‐
dure 1 (see the Supporting Information for details). Unless
otherwise noted, ratios were determined by GLC analysis
using tetracosane as an internal standard. Reactions were
With proper catalysts [5b]+[A]– identified (Table 1, entries 5
and 8), we assessed the functional‐group tolerance of the
method (Table 2). High yields and selectivities were obtained
for essentially any of the phenyl acetylene derivatives used
(1a–1k → 3aa–3ka; entries 1–11). The general trend was that
reactions were slower with electron‐withdrawing and vice
versa with electron‐donating substituents in the para posi‐
tion, providing early indication of a cationic intermediate
(for an intermolecular competition experiment, see the Sup‐
porting Information). However, the counteranion [A]‒ of the
catalyst had an influence on the selectivity. This generally
b
c
run until complete consumption of nBu3SnH; isolated yields
d
after filtration over Al2O3. 91% isolated yield were obtained
on a 1.0 mmol scale. eReaction was quenched after 48 h.
fRatio was determined by 1H NMR analysis (no baseline sepa‐
ration in the GLC analysis).
To understand the reaction mechanism, we began with an
investigation of the Sn–H bond activation. We had shown
before that the Ru–S bond in cationic Ohki–Tatsumi com‐
plexes [5]+[A]– splits dihydrogen10 as well as main‐group met‐
al hydrides with Si–H,11,12 B–H,14 and Al–H13 bonds into the
corresponding neutral ruthenium(II) hydride and the sulfur‐
stabilized main‐group electrophile. Hence, combining com‐
plexes [5]+[A]– and hydrostannanes 2 in CD2Cl2 at –78 °C
dropped to approx. 90:10 with [5b]+[BArF ]– but the high
4
selectivity previously seen in the model reaction was restored
with [5b]+[B(C6F5)4]–. Alkyl‐ and likewise silyl‐substituted
alkynes 1l–1s converted into alkynyl stannanes 3la–3sa exclu‐
sively (entries 12–19). An enyne reacted also in good yield (1t
→ 3ta; entry 20).—For comparison only, the hydrostannyla‐
tion of an internal alkyne was tested; at 80 °C, 1‐phenylprop‐
1‐yne afforded the vinyl stannane as a 3:1 mixture of regioi‐
somers (see the Supporting Information for details).
instantly
delivered
the
hydrostannane
adducts
[5∙R3SnH]+[A]–. These fleeting intermediates were fully char‐
acterized by NMR spectroscopy at –20 °C or –60 °C (Table
3).15 The observed hydride shifts at (1H) ~ –8.5 ppm and 2JH,P
coupling constants of ~48 Hz were similar to those found for
hydrosilane adducts.10b The Δ value in the 119Sn NMR spec‐
trum for the adduct formation of nBu3SnH (2a) is approx.
246 ppm, arising from –86.6 ppm for 2a to approx. +155 ppm
for [5∙nBu3SnH]+[A]– (entry 1 vs entries 3–6). Et3SnH (2b)
exhibited the same trend (entry 7), and Ph3SnH (2c) again
led to decomposition (entry 8). Those downfield shifts are
strong evidence for the formation of stannylium‐like electro‐
philes.16 For comparison, the resonance signal of neutral
DmpSSnnBu3 (Dmp = 2,6‐dimesitylphenyl) is at (119Sn) +79.6
ppm (entry 2), and other known heteroatom‐stabilized
stannylium ions are in the same range, e.g., (119Sn) +165 ppm
Table 2. Scope of the Dehydrogenative C(sp)–Sn Cou‐
plinga
for [nBu3Sn(OEt2)]+[BArF ]– (entry 9).16a The chemical shifts
4
of benzene‐coordinated [nBu3Sn(C6H6)]+ [B(C6F5)4]– and free
[nBu3Sn]+[BArF ]– have been detected at (119Sn) +263 ppm16b
and +356 ppm,146a respectively (entries 10 and 11).
entry alkyne 1
counter‐
3:4
yield of 3
anion [A]– (%)b
(%)c
1
1a (X = H)
[BArF ]–
[B(C6F5)4]– >99:1
[B(C6F5)4]– 99:1
>99:1
90d (3aa)
90 (3ba)
82 (3ca)
4
Table 3. Sn–H Bond Activation at the Ru–S Bond: 2JH,P
Coupling Constants as well as 1H and 119Sn NMR Shifts
of the Hydrostannane Adductsa
2
3e
1b (X = 4‐F)
1c (X = 4‐CF3)
4
1d (X = 4‐CO2Me) [BArF ]–
>95:5f 75 (3da)
4
5
1e (X = 4‐Cl)
1f (X = 4‐Br)
1g (X = 4‐OMe)
1h (X = 4‐Ph)
1i (X = 4‐Me)
1j (X = 3‐Me)
1k (X = 2‐Me)
1l (R = Bn)
[B(C6F5)4]– 96:4
[B(C6F5)4]– >95:5f 83 (3fa)
[B(C6F5)4]– >95:5f 85 (3ga)
86 (3ea)
6
7e
8
[B(C6F5)4]– 97:3
90 (3ha)
86 (3ia)
86 (3ja)
94 (3ka)
9
10
11
12
[BArF ]–
97:3
2JH,P
[Hz]
1H NMR 119Sn NMR
4
entry adduct
[BArF ]–
>99:1
>99:1
[ppm]
+4.7
—
[ppm]
–86.6
+79.6
4
[BArF ]–
1
nBu3SnH (2a)
DmpSSnnBu3
—
—
4
[BArF ]–
>95:5f 88 (3la)
2
4
ACS Paragon Plus Environment

Page 3 of 5
Journal of the American Chemical Society
1
2
3
4
5
6
7
8
9
3b
[5a∙nBu3SnH]+[BArF ]–
49.7
47.7
48.7
49.5
47.0
—
–8.6
–8.4
–8.6
–8.3
–8.4
—
+158.1
+156.5
+151.1
+154.5
+150.2
—
lish the C–C triple bond ([7]+[BArF ]– → 3, deprotonation
4
4
pathway). The resulting dihydrogen adduct [5∙H2]+[BArF ]– of
[5b∙nBu3SnH]+[BArF ]–
4
4
4
catalyst [5]+[BArF ]– eventually releases H2 gas, thereby com‐
4
5
6b
[5c∙nBu3SnH]+[BArF ]–
pleting the dehydrogenation.10 The vinyl stannane 4 is, if at
4
[5d∙nBu3SnH]+[BArF ]–
4
all, seen in minor quantities and likely stemming from the
7
8c
916a
1016b
1116a
[5b∙Et3SnH]+[BArF ]–
competing but disfavored hydride transfer ([7]+[BArF ]– → 4,
4
4
[5b∙Ph3SnH]+[BArF ]–
reduction pathway). To exclude the possibility of dehydro‐
genation followed by hydrogenation (1 → 3 → 4)22 or hydro‐
stannylation followed by dehydrogenation (1 → 4 → 3), we
performed two control experiments (Scheme 3). Catalyst
4
[nBu3Sn(OEt2)]+[BArF ]–
—
—
+165
4
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
[nBu3Sn(C6H6)]+[B(C6F5)4]–
—
—
+263
+360
[5b]+[BArF ]– was neither able to reduce the alkynyl stannane
[nBu3Sn]+[BArF ]–
—
—
4
4
(3aa → 4aa; top) nor to dehydrogenate the vinyl stannane
(4aa → 3aa; bottom).
aExperiments were performed in a J. Young NMR tube us‐
ing complexes [5]+[A]– (1.0 equiv) and hydrostannane 2 (1.2
equiv).bNMR characterization performed at –60 °C Decom‐
c
Scheme 2. Catalytic Cycle for the Dehydrogenative
Stannylation of Alkynesa
position was observed.
As for the hydrosilane activation,10b [5b]+[BArF ]– promoted
+
4
1H/2H scrambling between nBu3SnD (2a‐d1) and Et3SnH (2b).
In our hands, no deuterium exchange occurred in the ab‐
sence of the catalyst at 30 °C17 (see the Supporting Infor‐
mation for details).
[Ru]
SAr
R3P
H
Ph
[5·1]+
That proven Sn–H bond activation competes, however, with
the addition of the Ru–S bond across the C–C triple bond of
the substrate. Ohki and Tatsumi had described the adduct
– 1
+ 1
+
formation of [5]+[BArF ]– and an aryl‐ as well as an alkyl‐
[Ru]
SAr
4
R3P
substituted acetylene before;10a the molecular structure of the
[5]+
H–SnR3
H–H
resulting Markovnikov adduct [5∙PhCCH]+[BArF ]– with Ph3P
2
4
H
as ligand was crystallographically secured. The interconver‐
reduction
pathway
(hydro-
sion of [5b∙PhCCH]+[BArF ]– and [5b∙nBu3SnH]+[BArF ] by
H
4
4
R'
dissociative processes was then demonstrated by us (Scheme
1). Both setups, that is premixing [5b]+[BArF ]– with either
SnR3
+
+
stannylation)
4
4
[Ru]
[Ru]
SAr
phenyl acetylene (1a) or nBu3SnH (2a) prior to the addition
of the other reactant, led to the formation of the alkynyl
stannane 3aa (see the Supporting Information for details).
This is further evidence of the reversibility of both the addi‐
tion across the C–C triple bond and the Sn–H bond. We also
found that the reaction is faster starting from [5b∙nBu3SnH]+
[BArF ]–, indicating that the generation of [5b∙1a]+[BArF ]– is
SAr
SnR3
R3P
R3P
H
H
H
[5·H2]+
[5·2]+
SnR3
H
R'
R'
[Ru]
3
1
SAr
6
4
4
R3P
favored over [5b∙2a]+[BArF ]–.
deprotonation
pathway
(dehydro-
genation)
H
4
SnR3
H
Scheme 1. Competitive Activation of the Hydrostan‐
nane and the Terminal Alkyne
+
R'
[7]+
aThe BArF – counteranion was omitted for the sake of clarity.
4
Scheme 3. Attempted Hydrogenation of an Alkynyl
Stannane and Dehydrogenation of a Vinyl Stannane
Based on the above and our earlier12 observations, we deline‐
ate the following catalytic cycle (Scheme 2). Alkyne adduct
[5∙1]+[BArF ]– is an off‐cycle intermediate, reversibly convert‐
4
ing into the stannane adduct [5∙2]+[BArF ]– through catalyst
4
[5]+[BArF ]– (cf. Scheme 1). The stannylium‐ion‐like electro‐
4
phile [5∙2]+[BArF ]– is then nucleophilically attacked by the
4
C–C triple bond of 1 to yield a β‐tin‐stabilized18 vinyl cation19
along with the ruthenium(II) hydride 6. According to
Wrackmeyer’s work,20 that vinyl cation is best represented as
the bridged structure [7]+[BArF ]–. These neutral complexes 6
4
To summarize, we reported here the catalytic activation of
the Sn–H bond in hydrostannanes (tin hydrides) by hetero‐
lytic cleavage at the Ru–S bond of cationic ruthenium(II)
are rather poor hydride donors,21 and the sulfur atom in 6
serves as an internal Brønsted base instead.12 Hence, 6 ab‐
stracts the proton α to the tin atom in [7]+[BArF ]– to reestab‐
4
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 4 of 5
1
2
3
4
5
6
7
8
9
complexes. This cooperative bond activation11 leads to a
stannylium‐ion‐like tin electrophile together with the corre‐
sponding neutral ruthenium hydride. With this catalyst–
hydrostannane adduct terminal acetylenes are converted into
alkynyl stannanes; hardly any or no vinyl stannane is detect‐
ed. This outcome, that is the preference of dehydrogenation
over reduction, has been rationalized by the intermediacy of
a tin‐bridged vinyl cation which is deprotonated by the sul‐
fur atom in the ruthenium(II) hydride rather than reduced
by the ruthenium(II) hydride. The mild method is of broad
scope and a rare example of a direct C(sp)–H stannylation
with hydrostannanes.
(11) (a) Omann, L.; Königs, C. D. F.; Klare, H. F. T.; Oestreich, M.
Acc. Chem. Res. 2017, 50, 1258–1269. (b) Stahl, T.; Hrobárik, P.; Kö‐
nigs, C. D. F.; Ohki, Y.; Tatsumi, K.; Kemper, S.; Kaupp, M.; Klare, H.
F. T.; Oestreich, M. Chem. Sci. 2015, 6, 4324–4334.
(12) (a) Klare, H. F. T.; Oestreich, M.; Ito, J.‐i.; Nishiyama, H.; Oh‐
ki, Y.; Tatsumi, K. J. Am. Chem. Soc. 2011, 133, 3312–3315. (b) Königs,
C. D. F.; Klare, H. F. T.; Ohki, Y.; Tatsumi, K.; Oestreich, M. Org.
Lett. 2012, 14, 2842–2845. (c) Königs, C. D. F.; Müller, M. F.; Aigua‐
bella, N.; Klare, H. F. T.; Oestreich, M. Chem. Commun. 2013, 49,
1506–1508. (d) Hermeke, J.; Klare, H. F. T.; Oestreich, M. Chem. ‐ Eur.
J. 2014, 20, 9250–9254. (e) Omann, L.; Oestreich, M. Angew. Chem.,
Int. Ed. 2015, 54, 10276–10279.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(13) Forster, F.; Metsänen, T. T.; Irran, E.; Hrobárik, P.; Oestreich,
M. J. Am. Chem. Soc. 2017, 139, 16334–16342.
(14) Stahl, T.; Müther, K.; Ohki, Y.; Tatsumi, K.; Oestreich, M. J.
Am. Chem. Soc. 2013, 135, 10978–10981.
(15) Depending on the phosphine ligand, hydrostannane adducts
[5∙R3SnH]+[A]– decompose at room temperature within a few hours.
Sufficient chemical stability is secured at –20 °C or –60 °C, and NMR
spectra are meaningful at this temperature.
(16) (a) Kira, M.; Oyamada, T.; Sakurai, H. J. Organomet. Chem.
1994, 471, C4–C5. (b) Lambert, J. B.; Zhao, Y.; Wu, H.; Tse, W. C.;
Kuhlmann, B. J. Am. Chem. Soc. 1999, 121, 5001–5008. (c) Zharov, I.;
King, B. T.; Havlas, Z.; Pardi, A.; Michl, J. J. Am. Chem. Soc. 2000, 122,
10253–10254. (d) Lambert, J. B.; Lin, L.; Keinan, S.; Müller, T. J. Am.
Chem. Soc. 2003, 125, 6022–6023. (e) Wright II, J. H.; Mueck, G. W.;
Tham, F. S.; Reed, C. A. Organometallics 2010, 29, 4066–4070.
(17) Neumann and Sommer had reported rapid scrambling with‐
out a catalyst at 40 °C: Neumann, W. P.; Sommer, R. Angew. Chem.,
Int. Ed. 1963, 2, 547.
(18) For the β‐effect of the stannyl group in the stabilization of vi‐
nyl cations, see: Dallaire, C.; Brook, M. A. Organometallics 1990, 9,
2873–2874.
(19) For a recent review of vinyl cations, see: Vasilyev, A. V. Russ.
Chem. Rev. 2013, 82, 187–204 and cited references.
(20) Wrackmeyer, B.; Kundler, S.; Boese, R. Chem. Ber. 1993, 126,
1361–1370.
(21) Stahl, T.; Klare, H. F. T.; Oestreich, M. J. Am. Chem. Soc. 2013,
ASSOCIATED CONTENT
Supporting Information
1
Experimental details, characterization as well as H, 13C, 11B,
19F, 31P, and 119Sn NMR spectra. This material is available free
of charge via the Internet at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
martin.oestreich@tu‐berlin.de
ORCID
Francis Forster: 0000‐0002‐0364‐5491
Victoria M. Rendón López: 0000‐0002‐0056‐5787
Martin Oestreich: 0000‐0002‐1487‐9218
Notes
The authors declare no competing financial interests.
ACKNOWLEDGMENT
135, 1248–1251.
This research was in part supported by the Deutsche For‐
schungsgemeinschaft (Oe 249/8‐1). V.M.R.L. (on leave from
the University of Guanajuato, Mexico) thanks the Consejo
Nacional de Ciencia y Tecnología for a predoctoral fellowship
(No. 295157). M.O. is indebted to the Einstein Foundation
(Berlin) for an endowed professorship.
(22) Bähr, S.; Oestreich, M. Organometallics 2017, 36, 935–943.
REFERENCES
(1) Schaub, T. A.; Kivala, M. In Metal‐Catalyzed Cross‐Coupling
Reactions and More; de Meijere, A., Bräse, S., Oestreich, M., Eds.;
Wiley‐VCH: Weinheim, Germany, 2014, pp 665–762.
(2) The Stille Reaction; Farina, V., Krishnamurthy, V., Scott, W. J.;
Wiley: New York, 2004.
(3) Hartmann, H.; Honig, H. Angew. Chem. 1957, 69, 614 (R3SnCl
and R3SnBr with R = alkyl and aryl).
(4) Jones, K.; Lappert, M. F. J. Organomet. Chem. 1965, 3, 295–307.
(5) (a) Neumann, W. P.; Kleiner, F. G. Tetrahedron Lett. 1964, 5,
3779–3782. (b) Kleiner, F. G.; Neumann, W. P. Liebigs Ann. Chem.
1968, 716, 19–28.
(6) Kiyokawa, K.; Tachikake, N.; Yasuda, M.; Baba, A. Angew.
Chem., Int. Ed. 2011, 50, 10393–10396.
(7) Mitchell, T. N.; Moschref, S.‐N. Synlett 1999, 1259–1260.
(8) (a) Yoshida, H. Synthesis 2016, 48, 2540–2552. (b) Trost, B. M.;
Ball, Z. T. Synthesis 2005, 853–887.
(9) Toutov, A. A.; Betz, K. N.; Schuhman, D. P.; Liu, W.‐B.; Fe‐
dorov, A.; Stoltz, B. M.; Grubbs, R. H. J. Am. Chem. Soc. 2017, 139,
1668–1674.
(10) (a) Ohki, Y.; Takikawa, Y.; Sadohara, H.; Kesenheimer, C.; En‐
gendahl, B.; Kapatina, E.; Tatsumi, K. Chem. ‐ Asian J. 2008, 3, 1625–
1635. (b) Lefranc, A.; Qu, Z.‐W.; Grimme, S.; Oestreich, M. Chem. ‐
Eur. J. 2016, 22, 10009–10016.
ACS Paragon Plus Environment

Page 5 of 5
Journal of the American Chemical Society
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
5
ACS Paragon Plus Environment