Highly selective hydrosilylation of equilibrating allylic azides

Article abstract of DOI:10.1039/d0cc01316a

The Pt-catalyzed hydrosilylation of equilibrating allylic azides is reported. The reaction provides only one out of four possible hydrosilylation products in good yields and with very high chemoselectivity (alk-1-enevs.alk-2-ene), regioselectivity (linearvs.branched), and excellent functional group tolerance.

Full text of DOI:10.1039/d0cc01316a

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DOI: 10.1039/D0CC01316A
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Highly selective hydrosilylation of equilibrating allylic azides
Ruzhang Liu,* Zhen Wei, Juan Wang, Yongmei Liu and Huaiguo Xue
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
G
The Pt-catalyzed hydrosilylation of equilibrating allylic azides is
reported. The reaction provides only one out of four possible
hydrosilylation products in good yields and with very high
chemoselectivity (alk-1-ene vs alk-2-ene), regioselectivity (linear vs
branched), and excellent functional group tolerance.
G
R
k1
R
R
N3
N3
or
N3
G
Alk-2-ene
Alk-2-ene's
product
Primary azide's
product
Primary azide
k2
G
G
N3
N3
N3
k3
R
or
R
R
G
The rearrangement of allylic azides, which is first discovered by
Winstein and co-workers in 1960, provides an interesting
platform for studying the relative reactivity of different types of
azides and olefins.1 However, this rearrangement generally
produces a mixture of constitutionally isomeric allylic azides
consisting of alk-1-ene isomer featuring the secondary azide as
well as trans- and cis-alk-2-ene isomers both featuring the
primary azide (Fig. 1, top). Thus, this reaction has seen limited
synthetic applications because of the generation of mixtures of
olefin and azide products, thereby prohibiting subsequent
transformations.2,3 In order to achieve the selective capture of
alk-1-ene isomer in the downstream reactions, k3 and k2 must
be much faster than k1 (Fig. 1, top). At the same time, the
relative difference between k2 and k3 is less significant than that
of k1, while the branched alk-1-ene isomer is considerably more
useful than either of the linear alk-2-ene isomers. For metal-
catalyzed reactions, the strong coordination of the azide group
makes metal binding easier than the alternative binding of the
metal to the olefin or other reactive partners (Fig. 1., top). This
in turn inhibits the catalytic cycle, greatly increasing the
difficulty of achieving synthetically useful selectivity in allylic
azide rearangement reactions. Although allylic azide isomers
have been successfully differentiated in intramolecular
reactions by tuning the distance between a reactive site and
azide/olefin,4 the selectivity in significanlty more synthetically
valuable intermolecular reactions of allylic azides has not been
accomplished to date. 5 These reactions could lead to the
Alk-1-ene's
product
Secondary azide's
product
Alk-1-ene
Secondary azide
 Competitive binding modes for metal-catalyzed reactions
M
M
N
N
N
R
vs
Ph
N
R
N
N
N
N
AAC
+
N
R
two examples
Ph
50:50 to 72:28
N3
Epoxidation
O
R
R
+
R
N3
N3
two examples
O
67:33 to >95:5
'Pd'
O
Wacker
oxidation
R
N3
O
N3
N3
R
R
+
+
R
one example
H
N3
R
O
unstable
[Si]
54% (5:1)
'Pt'
N3
N3
Hydrosilylation
N3
R
this work
[Si]
R
single product
[Si]
not observed
Fig. 1 Selective reactions of equilibrating allylic azides.
synthesis of nitrogen-functionalized alk-1-ene derivatives that
would be difficult to access by existing methods. For example,
the difference between primary and secondary azides in allylic
azide isomers cannot be distinguished in the azide-alkyne
cycloaddition reaction (AAC) (Fig. 1, bottom), while the more
electron-rich nature of disubstituted than monosubstituted
olefin has been exploited in epoxidation reactions.5a
Furthermore, in the palladium-catalyzed Wacker oxidation of
a. College of Chemistry & Chemical Engineering, Yangzhou University, 180
Siwangting Rd. Yangzhou 225002, China. E-mail: liurzh@yzu.edu.cn.
†Electronic Supplementary Information (ESI) available: Supporting tables, allylic azide isomers, the derivatized product of alk-1-ene
experimental procedures, characterization data, and copies of NMR spectra. See
DOI: 10.1039/x0xx00000x
isomer has been observed; however, this azidoaldehyde is
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Table 1 Preparation and selective hydrosilylation of equilibrating allylic azides.a
unstable, leading to the overall low selectivity of the
rearrangement (Fig. 2, bottom).5b,6 Thus, the selective capture
of one of the allylic azide isomers, especially the synthetically
more useful branched alk-1-ene isomer, in an intermolecular
downstream reaction would significantly improve the synthetic
applicability of allylic azides. More importantly, the selective
differentiation of alk-1-ene over alk-2-ene of allylic azide
mixtures in a subsequent olefin hydrofunctionalization7 would
provide very useful functionalized secondary azides, which
typically require multiple steps by conventional methods.8
Herein, we report that differentiating the reactivity of alk-1-
ene over alk-2-ene can be achieved by merging the allylic azide
rearrangement with olefin hydrosilylation. Strikingly,
equilibrating allylic azides afford one out of the four possible
hydrosilylation products in this novel process.
View Article Online
DOI: 10.1039/D0CC01316A
SiMe2Ph
1. HG-2
allyl bromide
k4
Bn
N3
2a
2b
Bn
Bn
N3
trans-Alk-2-ene:
cis-Alk-2-ene:
3a
2. NaN3
60%
1
Catalyst,
PhMe2SiH
N3
k5
Bn
N3
k6
k7
3b
SiMe2Ph
Bn
N3
2c
Alk-1-ene:
Bn
mixture
SiMe2Ph
b
3c
2a 2b 2c
:
(
:
= 60:10:30)
Cat.
Loading
(mol%)
5
10
1.5
10
10
2
0.25
Yield
of 3c
(%)c
76
70
71
28
65
58
86e
Ratio
Entry
Catalyst
Solvent
3c:(3a+3b)d
1
2
3
4
5
6
7
Karstedt’s cat.
(COD)PtCl2
Pt(dba)3
H2PtCl46H2O
K2PtCl4
THF
Toluene
MTBE
Toluene
Toluene
Toluene
Toluene
> 30:1
> 30:1
> 30:1
> 30:1
> 30:1
> 30:1
> 30:1
The alkene hydrosilylation is one of the most industrially used
transformations for upgrading commodity alkenes.7 Among
various catalysts, Pt-based complexes are employed most
frequently due to their high reactivity, good anti-Markovnikov
selectivity, and broad functional group compatibility.9 Among
Marko’s cat.
Karstedt’s cat.
a Conditions: 2 (0.3 mmol), PhMe2SiH (4.0 equiv.), solvent (2.5 mL), 90 oC, 36 h.
Determined by 1H NMR in CDCl3. c Isolated yield. d Only one isomer observed by 1H
b
many challenges to achieve high selectivity in hydrosilylation of NMR. e 70 oC, 24 h.
equilibrating allylic azides, the catalytic system must be
MesN
NMes
Cy
compatible with the sensitive azide group.10 It is well known
that azides can react with most transition metals to form imido
complexes, thus inhibiting the catalytic turnover.11 Moreover,
widely used phosphine ligands in transition-metal-catalysis can
react with azides, e.g. Staudinger reaction, thus losing their
ability to tune the transition metal.12 These challenges are
exacerbated because of the temperatures required in order to
accelerate the allylic azide rearrangement.1c,3 Thus, the
successful implementation of selective hydrosilylation of
equilibrating allylic azides heavily relies on the compatibility
between the catalytic system and the allylic azide as well as the
faster hydrosilylation rate of alk-1-ene than alk-2-ene, whereas
the linear/branched selectivity must also be considered.
As shown in Table 1, alkene 1 was reacted with allyl bromide
via alkene cross metathesis using the Hoveyda-Grubbs catalyst
2nd generation (HG-2) to give the corresponding allylic
bromide, which without purification was subjected to the
subsequent azide displacement to afford trans-alk-1-ene 2a,
which rapidly rearranged at room temperature and reached a
steady-state equilibrium of allylic azides with 60:10:30 ratio of
three constitutional isomers 2a, 2b, and 2c.4b Initially, we
conducted the hydrosilylation of allylic azdie 2 catalyzed by the
Co(acac)2/xantphos system without any reaction, while the de-
azidation mixture of 1-alkene and 2-alkene was obtained by the
Fe/OIP-catalyzed hydrosilylation.13 Then we turned our
attention to Pt-based Karstedt’s catalyst, which has been used
as a benchmark in many industrial hydrosilylations.9 The
reaction of 2 with 4.0 equiv of tertiary silane PhMe2SiH was
carried out with 5 mol% of Karstedt’s catalyst at 90 °C, and
afforded 76% of 3c, the anti-Markovnikov hydrosilylation
product (entry 1, Table 1). Remarkably, we did not observe 3a,
resulting from hydrosilylation of 2a or 2b,14 nor 3b, the
Markovnikov hydrosilylation product of 2c (1H NMR analysis).
The overall yield of 76% exceeded the percentage (30%) of 2c in
Si
Si
Cl
Si
Si
N
Si
Si
Ru
Pt
O
Pt
Pt
O
O
O
Cl
N
Si
Si
O
Cy
Markó's cat.
Karstedt's cat.
HG-2
the starting allylic azide 2, thus indicating that k4 and k6 must be
much slower than k7. These results demonstrate that the rate
differentiation of alk-1-ene over alk-2-ene is realized in the
hydrosilylation of equilibrating allylic azides. Examination of
other Pt-based complexes, such as (COD)PtCl2, Pt(dba)3,
H2PtCl66H2O, K2PtCl6 and even Marko’s catalyst,15 gave lower
yields (entries 2-6, Table 1). After further screening (Table S1,
ESI), 0.25 mol% of catalyst loading was established as optimal
(entry 7, Table 1). Importantly, this suggests that the azide
group influences the efficiency of catalyst only to some extent
in comparison to the reported olefin hydrosilylation.16 This
reaction underwent smoothyl on 5 mmol scale to afford 3c in
84% isolated yield.
With the optimal reaction conditions established, we
examined the substrate scope of this novel protocol (Scheme 1).
Importantly, in all cases, only one linear regioisomer in this
hydrosilylation was observed out of the three or four
interconverting allylic azide isomers. After simple conversion to
allylic azides, feedstock olefins were transformed into
functionalized 3-azidopropansilanes 4-9 in good yields. The
reaction is compatible with a wide range of functional groups,
including internal olefins (10), ketones (11, 12, 26, 28), esters
(13, 14, 15, 26), amides (16), carboxylic acids (17), ethers (18),
azides (19), tosyl amides (20, 21), imides (22), epoxides (23, 24,
25), and even ketals (27). The diastereoselectivity resulting from
the existing stereocenters (10, 23-28) is low when the newly-
built azido stereocenter is adjacent to the existing stereocenter
(23). Modest selectivity is observed for 27 when methyl group
was introduced at the 2-position of allylic azides. Importantly,
2 | J. Name., 2012, 00, 1-3
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R
N3
Karstedt's cat. (0.25 mol%)
PhMe2SiH (4.0 equiv)
N3
View Article Online
DOI: 10.1039/D0CC01316A
R
SiMe2Ph
Toluene, 70 oC, 24-36h
N3
only one isomer
4-36
R
yield (dr)b
mixture
N3
N3
N3
N3
N3
N3
SiMe2Ph
Ph
SiMe2Ph
Me
SiMe2Ph
Me
SiMe2Ph
SiMe2Ph
4
SiMe2Ph
4
5
6
7
8
9
70%
90%
66%
85%
57%
77%
N3
N3
N3
O
N3
N3
MeOOC
N3
Me
EtO
SiMe2Ph
AcO
SiMe2Ph
SiMe2Ph
Ph
SiMe2Ph
SiMe2Ph MeOOC
SiMe2Ph
Me Me
O
O
10
11
55%
12
71%
13
97%
14
55%
15
54%
66% (1:1 dr)
N3
N3
N3
N3
Me
N3
N3
H
N
H2N
HO
O
N3
N
SiMe2Ph
SiMe2Ph
Ph
SiMe2Ph
SiMe2Ph
Ts
SiMe2Ph Ts
SiMe2Ph
O
O
16
40%
17
53%
18
57%
19
81%
20
69%
21
68%
O
N
O
O
N3
N3
N3
N3
N3
N3
COOEt
O
O
SiMe2Ph
SiMe2Ph
SiMe2Ph
SiMe2Ph
SiMe2Ph
SiMe2Ph
O
O
O
Me
26
27
79% (32:28:18:22 dr)
22
80%
23
24
25
35% (1:1:1:1 dr)c
90% (1:1 dr)
68% (1:1 dr)
81% (1:1 dr)
O
Me
H
N3
N3
H
Ph
[Si]
N3
N3
32
33
34
35
36
81% ([Si] = Et3Si)
SiMe2Ph
H
EtOOC
SiMe2Ph
Ph
SiMe2Ph
PhMe2Si
81% ([Si] = Ph2MeSi)
83% ([Si] = Ph3Si)
Ph
29
50%
O
30
NR
31
N3
81% ([Si] = (EtO)3Si)
71% ([Si] = tBuMe2Si)d
NR
28
63% (1:1 dr)
Scheme 1 Substrate scope. a Conditions: allylic azides (0.3-0.5 mmol), PhMe2SiH (4.0 equiv.), Karstedt’s catalyst (0.25 mol%), toluene (2.5 mL), 70 oC, 24-36 h. b Isolated yield, and
diastereomeric ratio determined by 1H NMR if applied. c 1:1 dr of 3-vinyl-7-oxabicyclo[4.1.0]heptane was employed. d Condition: Karstedt’s catalyst (2 mol%), 90 oC, 48 h.
O
no reaction occured. Although the phenyl group at the 2-
N3
1. H2, Pd/C, EA, 74%
HN
Ph
position of allylic azides is still conjugated with the olefin, it
doesn’t influence the allylic azide rearrangement, leading to 29
in 50% yield. Examination of other tertiary silanes, such as
2. benzoyl chloride
Et3N, DCM
Ph
SiMe2Ph
Ph
SiMe2Ph
39
3c
70%
Ph
triethylsilane,
diphenylmethylsilane,
triphenylsilane,
CuSO4 5H2O,
sodium L-ascorbate
tBuOH/H2O (1:1)
12 h, 71%
1. HBF4 Et2O, DCM,
0 oC, 12 h
triethoxylsilanes, and tert-butyldimethyl silane, resulted in the
formation of the corresponding products 32-36 in high yields in
all cases.
2. KF, H2O2, NaHCO3,
MeOH/THF, 12 h, rt
58%
Ph
N
N
N
N3
To further demonstrate the synthetic utility of this new
reaction, we utilized the copper-catalyzed AAC reaction to
convert 3c into triazole 37 in 71% yield (Scheme 2).17 Next,
hydrogenation and acylation afforded amide 39 in 70% yield.
Finally, although conversion of silane to the hydroxyl group was
initially problematic because of the low stability of the azide
group to acidic conditions,18 after short optimization (Table S3,
ESI), 1,3-azido alcohol 38 was obtained in 58% yield along with
12% of 3-hydroxy ketone as the degradation product of azide
group. These reactions clearly demonstrate the bi-functional
properties of -azido-silanes produced in this tandem allylic
azide rearrangement/hydrosilylation process.
In summary, the Pt-catalyzed hydrosilylation of equilibrating
allylic azides provides only one out of four possible
hydrosilylation products in good yields and with very high
chemoselectivity (alk-1-ene vs alk-2-ene), regioselectivity
(linear vs branched), and very good functional group tolerance.
Ph
SiMe2Ph
Ph
OH
37
38
Scheme 2 Conversions of 3-azidopropylsilane 3c.
this protocol can be used to modify complicated drug
molecules. For example, estrone was converted to the silicon-
functionalized azide 28 in 63% yield.
For most allylic azides, the ratio of alk-1-ene isomer ranges
from 6% (S21) to 48% (S25), and is influenced by adjacent
substituents (Table S2, ESI). When the substituent is larger and
closer to the allylic azide moiety, the ratio of alk-1-ene isomer
drops (e.g. 23 vs. 24). The introduction of groups at the 2-
position of allylic azides significantly increases the ratio of alk-
1-ene isomer (e.g. 27). The allylic azide rearrangement is
prevented by conjugation with arenes or carbonyl derivatives,
such as when the hydrosilylation failed to afford 30 and 31 with
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Journal Name
E.-C. Liu and J. J. Topczewski, J. Am. Chem. Soc., 2019, 141,
In combination with the facile preparation of allylic azides from
simple and abundant olefins, this mild and general protocol
provides rapid access to a diverse array of 3-azidopropylsilanes.
These compounds serve as bi-functional handles featuring the
versatile azide and silicon functional groups. Efforts to develop
an asymmetric version of this reaction are currently underway
in our laboratory.
We thank Professor Jeffrey Aubé for helpful discussions and
providing allylic azides S24-3, S25-5, S27-3, and S28-2. This work
was financially supported by the National Natural Science
Foundation of China (No 21472161), the Priority Academic
Program Development of Jiangsu Higher Education Institutions
(No. BK2013016), and Top-notch Academic Programs Project of
Jiangsu Higher Education Institutions (No. PPZY2015B112). We
thank Jing Liang, Yacheng Zhu and Shuai Zhu for synthetic
assistance. The analytical center of Yangzhou University is
acknowledged for analytical assistance.
View Article Online
5135-5138.
7
8
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Conflicts of interest
There are no conflicts to declare.
9
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2
3
4
For recent mechanistic studies of Weinstein rearrangement,
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P. Suding, C. J. Cramer and J. J. Topczewski, J. Org. Chem., 2018,
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(a) D. Craig, J. W. Harvey, A. G. O'Brien and A. J. P. White, Org.
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McArdle and P. V. Murphy, Synthesis, 2017, 49, 2138-2152; (f)
M. R. Porter, R. M. Shaker, C. Calcanas and J. J. Topczewski, J.
Am. Chem. Soc., 2018, 140, 1211-1214.
16 C. J. Kong, S. E. Gilliland, B. R. Clark and B. F. Gupton, Chem.
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18 (a) J. Aubé and G. L. Milligan, J. Am. Chem. Soc., 1991, 113,
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6
(a) A. K. Feldman, B. Colasson, K. B. Sharpless and V. V. Fokin,
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Recently, the dihydroxylation and copper-catalyzed AAC were
utilized by Topczewski to achieve dynamic kinetic resolution
of inter-converting cyclic allylic azides, but the regio-
selectivity was not applied. See: (a) A. A. Ott, C. S. Goshey and
J. J. Topczewski, J. Am. Chem. Soc., 2017, 139, 7737-7740; (b)
4 | J. Name., 2012, 00, 1-3
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