Palladium-Catalyzed Oxidative Dehydrosilylation for Contra-Thermodynamic Olefin Isomerization

Article abstract of DOI:10.1021/acscatal.0c02697

We report a newly developed, palladium-catalyzed dehydrosilylation of terminal alkylsilanes that combines with chain-walking hydrosilylation to create a one-pot isomerization of internal olefins to terminal olefins. This catalytic dehydrosilylation is one of the few examples of thermal catalytic functionalizations of unactivated alkylsilanes. The reaction involves transmetalation of an alkylsilane, β-hydride elimination, release of the terminal olefin, and reoxidation of the palladium catalyst. A variety of linear internal olefins underwent the overall isomerization to terminal olefins in good yields and in good regioselectivities. Particularly noteworthy, isomerizations occurring over seven carbon units proceeded in yields that are comparable to those of isomerizations occurring over one carbon unit.

Full text of DOI:10.1021/acscatal.0c02697

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Letter
Palladium-Catalyzed Oxidative Dehydrosilylation
for Contra-Thermodynamic Olefin Isomerization
Steven Hanna, Tyler Wills, Trevor W Butcher, and John F. Hartwig
ACS Catal., Just Accepted Manuscript • DOI: 10.1021/acscatal.0c02697 • Publication Date (Web): 21 Jul 2020
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Palladium-Catalyzed Oxidative Dehydrosilylation for Contra-Thermo-
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Steven Hanna, Tyler Wills, Trevor W. Butcher, and John F. Hartwig*
Division of Chemical Sciences, Lawrence Berkeley National Laboratory, and Department of Chemistry, University of Cali-
fornia, Berkeley, California 94720, United States
olefin isomerization • contra-thermodynamic • chain-walking • remote functionalization • retro-hydrofunctionalization •
oxidative palladium reactions
ABSTRACT: We report a one-pot isomerization of internal olefins to terminal olefins that proceeds through chain-walking hydros-
ilylation followed by a newly developed, palladium-catalyzed dehydrosilylation of terminal alkylsilanes. This catalytic dehydrosi-
lylation is one of the few examples of thermal catalytic functionalizations of unactivated alkylsilanes. The reaction involves
transmetalation of an alkylsilane, β-hydride elimination, release of the terminal olefin, and re-oxidation of the palladium catalyst. A
variety of linear internal olefins underwent the overall isomerization to terminal olefins in good yields and in good regioselectivities.
Notably, isomerizations occurring over seven carbon units proceeded in yields that are comparable to those of isomerizations occur-
ring over one carbon unit.
Internal olefins are more thermodynamically stable than termi-
nal olefins. Therefore, isomerizations of terminal olefins to in-
ternal olefins are exergonic, and many strategies to conduct
Scheme 1. Challenges Facing Catalytic Dehydrosilylation
and Design of a Catalytic Oxidative Dehydrosilylation
1
such isomerizations have been reported. However, strategies
for the contra-thermodynamic isomerization of internal olefins
to terminal olefins remain underdeveloped. Most strategies for
contra-thermodynamic, positional isomerization of alkenes in-
volve allylic functionalization followed by defunctionalization
2
with allylic transposition; however, these approaches enable
translocation of a double bond by a maximum of only one car-
bon unit and require harsh reagents. Strategies for long-range,
contra-thermodynamic olefin isomerizations, i.e. those that oc-
3
cur through two or more carbon units, typically produce termi-
nal alkenes in low yields and/or in low selectivities. A mild
method for the contra-thermodynamic, long-range translocation
of carbon-carbon double bonds could enable the valorization of
mixtures of internal olefins to single isomers of terminal olefins,
the late-stage derivatization of complex molecules containing
internal olefins, and the installation of functional groups at sites
that are remote from the initial position of the double bond.
A variety of transition-metal catalyzed, chain-walking hydro-
functionalizations could potentially be combined with dehy-
drofunctionalizations to enable such long-range, contra-thermo-
4
dynamic olefin isomerizations. We previously reported a one-
pot process for the selective, long-range isomerization of inter-
nal olefins to terminal olefins involving platinum-catalyzed,
chain-walking hydrosilylation of internal olefins with tri-
chlorosilane followed by a formal, reagent-based retro-hydros-
5
ilylation of the resulting terminal alkylsilanes (eq 1).
Platinum-catalyzed hydrosilylation occurs with high n:iso ra-
tios, low loadings of catalyst, and without need for solvent, but
the formal retro-hydrosilylation we developed comprises three
uncatalyzed reactions: conversion of the terminal alkylsilane to
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a pentafluorosilicate, iodination of the silicate, and base-pro-
Page 2 of 6
times at this temperature did not significantly improve the yield
(entry 2). Olefin 3b formed in similar yields at 140 °C and 120
°C (entry 3). Olefin 3b formed in much lower yields at 100 °C
and 80 °C (entries 4-5), but these lower yields were simply due
to slower rates. The yields of reactions at 100 °C and 80 °C were
higher when the reaction was conducted for 20 h, rather than for
15 min (entries 6-7), and the yield of the reaction at 100 °C after
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moted elimination. This formal retro-hydrosilylation occurred
in good yield, but each step required an excess of reagents. If
any of these steps could be replaced by a catalytic process or,
preferably, if multiple uncatalyzed steps could be combined in
a single catalytic cycle, then the overall sequence would be
more atom-efficient and operationally simple.
2
0 h was similar to that at 140 °C for 15 min (entry 6).
However, several factors make the development of a catalytic
dehydrosilylation difficult (Scheme 1). Simple catalytic retro-
hydrosilylation without coupling to additional exergonic pro-
cesses is unlikely to occur because dehydrosilylation is substan-
Table 1. Catalytic dehydrosilylation of linear alkylsilanes
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tially disfavored thermodynamically (Scheme 1A). Even a cat-
alytic transfer dehydrosilylation involving the microscopic re-
verse of hydrosilylation and addition of silane to a strained ac-
ceptor, e.g. norbornene, would be challenging because the oxi-
dative addition of a C–Si bond that would occur to initiate the
reverse of a Chalk-Harrod mechanism is an uncommon elemen-
tary step and because the oxidative addition of the b-C–H bond
that would initiate the reverse of a modified Chalk-Harrod
mechanism would be unlikely to occur selectively in the pres-
ence more accessible C–H bonds (Scheme 1B). Addition of a
C–H bond other than the b-C–H bond would likely lead to de-
hydrogenation, rather than dehydrosilylation. Moreover, any
retro-hydrosilylation applied to contra-thermodynamic olefin
isomerization should occur under conditions that are irreversi-
ble and that lack a persistent hydride because equilibrating con-
ditions and the presence of persistent metal-hydrides would
likely lead to the isomerization of terminal olefins to internal
olefins. Alternative pathways could involve cleavage of the C–
Si bond by steps other than those in a microscopic reverse of
hydrosilylation, but catalytic reactions that cleave unactivated
7
alkyl–Si bonds under thermal conditions, including transmeta-
8
lations of alkylsilanes to enable cross-couplings, are rare.
To address these challenges, we envisioned an oxidative dehy-
drosilylation that draws analogies to oxidative dehydrogena-
tion, by which endergonic alkane dehydrogenations are coupled
9
with the exergonic reduction of O
2
to water. In this case, the
reaction design could involve transmetallation to cleave the C–
Si bond, thereby creating more favorable kinetics if the oxida-
tion step is fast.
We report the realization of such a process in the form of a pal-
ladium-catalyzed oxidative dehydrosilylation of primary al-
kylsilanes to form a-olefins with benzoquinone (BQ) as oxidant
Olefin 3b formed in low yields in the presence of fluoride
sources other than CsF (entries 8-9). The yields and regioselec-
tivities of the reaction were similar when the reaction was con-
ducted with ten, eight, or six equivalents of CsF (entries 1, 10-
11). Even with five equivalents of CsF, olefin 3b formed in 58%
yield (entry 12). However, olefin 3b formed in low yields when
the reaction was conducted with four or fewer equivalents of
CsF (entry 13). The reaction with two equivalents of benzoqui-
none occurred in approximately the same yield as that with
three equivalents (entry 14). Reactions conducted with catalyst
loadings as low as 1 mol% occurred in yields and regioselectiv-
ities that were only slightly lower than those in entry 1 (entries
15-17). (entry 17).
(Scheme 1C). This dehydrosilylation occurs in good yields with
good selectivity for the 1-alkene and combines with chain-
walking hydrosilylation to transform internal alkenes to termi-
nal alkenes with translocation of the double bond through mul-
tiple carbon units. To develop a catalytic oxidative dehydrosi-
lylation, we envisioned that the process could occur by the
mechanism in Scheme 1C. Transmetalation of the alkylsilane to
an electrophilic late transition-metal complex would generate
an alkyl complex that could undergo β-hydride elimination to
release the product and produce a metal hydride. This hydride
could react with an oxidant to regenerate the starting electro-
10
philic complex.
To assess the viability of the proposed reaction, we conducted
the oxidative dehydrosilylation of octadecyl trichlorosilane (2a)
under the conditions shown in Table 1. A series of experiments
varying the conditions of this reaction showed that alkylsilane
2a reacts with benzoquinone and cesium fluoride in the pres-
Olefin 3b formed in lower yields when the reaction was con-
ducted in DMSO, THF, or toluene than when the reaction was
conducted in dioxane (entries 18-20), and olefin 3b formed in
slightly lower yields when the reaction was conducted with
2 2 3
Pd(OAc) as the pre-catalyst rather than with Pd dba as the pre-
ence of Pd
2 3
dba at 140 °C to form olefin 3b in 67% yield (Table
catalyst (entry 21). Finally, little change in yield was observed
1, entry 1). The reaction proceeded in 15 min; longer reaction
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when the reaction was conducted under conditions that were
In addition, many common functional groups are incompatible
with platinum-catalyzed chain-walking hydrosilylation with tri-
chlorosilane because this silane is a powerful reducing agent,
and Speier’s catalyst is highly active. Thus, ketones and esters
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more dilute than those in entry 1 (entry 22).
We also sought to determine whether our newly developed cat-
alytic dehydrosilylation of linear alkylsilanes could be con-
ducted on the crude product of a chain-walking hydrosilylation
to enable a one-pot isomerization of internal olefins to terminal
7
f,12
underwent reduction under the reaction conditions.
Olefins
bearing tertiary amines also did not undergo the reaction, form-
ing precipitates immediately upon addition of trichlorosilane at
room temperature. Thus, chain-walking hydrosilylations with
silanes other than trichlorosilane and with catalysts enabling
milder conditions are needed and are currently being sought.
4c-f,11
olefins. To do so, we reacted internal alkenes with varying
geometries and with double bonds present at different positions
along the chain with two equivalents of trichlorosilane in the
presence of Speier’s catalyst (0.1 mol%), evaporated the vola-
tile materials, and subjected the crude reaction mixtures to con-
ditions for dehydrosilylation.
Nonetheless, the catalytic dehydrosilylation we have developed
has several advantages over the iodinative dehydrosilylation we
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reported recently. The iodinative process occurs in two sequen-
The results in Table 2 show that this sequence leads to the con-
version of 2-, 3-, and 4- alkenes, as well as deeply embedded
alkenes, to the terminal 1-isomers. Specifically, internal octenes
tial steps (iodination and base-promoted elimination), while the
catalytic dehydrosilylation reported here forms terminal olefins
from alkylsilanes in a single step. In addition, the catalytic de-
hydrosilylation requires fewer equivalents of reagents than the
iodinative process because the additional base-promoted elimi-
nation step of the iodinative process is not required. Further im-
provements to the atom efficiency of the new catalytic process
are underway.
1c, 1d, and 1e underwent isomerization to 1-octene (olefin 3c)
in good yields. The results with this set of octenes also show
that both (E) and (Z) alkenes undergo the olefin transfer process.
Moreover, translocation of the double bond over seven posi-
tions occurred in yields similar to those for transfer over fewer
positions. Specifically, trans-7-tetradecene (olefin 1f) under-
went isomerization to form 1-tetradecene (olefin 3f) in good
yield.
To elucidate the factors controlling the rate of the dehydrosi-
lylation, preliminary mechanistic experiments connecting the
identity of the silyl group to the rate of transmetalation were
conducted (Scheme 2). Trialkoxysilane 2a’ did not undergo pal-
ladium-catalyzed dehydrosilylation, even in the presence of a
fluoride activator. However, unactivated trifluoroalkylsilanes
and unactivated pentafluoroalkylsilicates are known to undergo
Hiyama couplings with aryl and vinyl electrophiles in the pres-
Table 2: One-pot contra-thermodynamic isomerizations of
internal olefins to α-olefins
8b-d
ence of fluoride activators. Trifluoroalkylsilanes are thought
to form alkylpentafluorosilicates in situ prior to transmetalation
8
c
and hexafluorosilicate salts after transmetalation. We have
verified that trifluorooctadecylsilane (2a’’), prepared from al-
kylsilane 2a, undergoes dehydrosilylation under the reaction
conditions in Table 1. Since the dehydrosilylation proceeds in
low yields in the presence of a low number of equivalents of
fluoride and gives no alkene in the absence of fluoride, al-
kylsilane 2a likely undergoes nucleophilic substitution with flu-
oride to form a pentafluorosilicate prior to transmetalation.
13
These data point to strongly nucleophilic silanes, and silanes
8
e
containing donating groups as potential reagents for the chain-
walking hydrosilylation that would dovetail with catalytic de-
hydrosilylation to create an olefin isomerization with broader
scope.
Scheme 2. Preliminary Studies on the Effect of Silane
As a new class of reaction, this oxidative dehydrosilylation does
have several limitations that must be addressed for broad ap-
plicability. For example, β-branched silanes underwent dehy-
drosilylation in low yields, presumably because the additional
steric bulk at the β position inhibited transmetalation. One long-
term goal is the isomerization of alkenes in natural products,
such as terpenes, which contain trisubstituted alkenes bearing
methyl substituents. Such alkenes would form β-branched
silanes by chain-walking hydrosilylation. Thus, catalysts that
undergo more rapid transmetalation would enable isomerization
in such natural products, and the development of such catalysts
is ongoing.
On the basis of these data, we propose the catalytic cycle in
Scheme 3 in which a trichloroalkylsilane undergoes nucleo-
philic substitution with fluoride to form a pentafluorosilicate,
transmetalation of this species to palladium, followed by β-hy-
dride elimination, dissociation of alkene, and re-oxidation of
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palladium by benzoquinone to form the conjugate base of hy-
droquinone (HBQ ) and to regenerate the active catalyst, alt-
Steven Hanna gratefully acknowledges Chevron for a predoctoral
fellowship, and Trevor W. Butcher gratefully acknowledges the
National Science Foundation for a predoctoral fellowship. We also
acknolwedge the UC Berkeley NMR facility and the National In-
stitutes of Health for providing funding for the cryoprobe for the
AV-600 spectrometer under grant S10OD024998.
-
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hough the precise fate of the reduced BQ is not known. The
identity of the ancillary ligands and the X groups on palladium
are unknown. However, given the high concentration of fluo-
ride in the system, the X groups on palladium are likely fluo-
rides.
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Scheme 3. Proposed Catalytic Cycle for the Oxidative De-
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oxidation to the alcohol. This catalytic functionalization in-
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and H NMR Spectra of products (Table 2) This material is avail-
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AUTHOR INFORMATION
Corresponding Author
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of Halogenated Aliphatic Hydrocarbons with Carbon Dioxide. Nature
*
Prof. J. F. Hartwig
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Department of Chemistry, 718 Latimer Hall
University of California, Berkeley
Berkeley, CA 94708
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Chem. Soc. 1961, 83, 1351. (d) Bank, H. M.; Saam, J. C.; Speier, J. L. The
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jhartwig@berkeley.edu
ORCID
Steven Hanna: 0000-0002-1005-3873
John F. Hartwig: 0000-0002-4157-468X
Author Contributions
Notes
The authors declare no competing financial interest.
Funding Sources
Isomerization–Hydroboration:
A
Strategy
for
Remote
This work was supported by the Director, Office of Science, U.S.
Department of Energy, under contract no. DE-AC02-05CH1123.
Hydrofunctionalization with Terminal Selectivity. J. Am. Chem. Soc. 2013,
135, 19107. (j) Palmer, W. N.; Diao, T.; Pappas, I.; Chirik, P. J. High-
Activity Cobalt Catalysts for Alkene Hydroboration with Electronically
Responsive Terpyridine and α-Diimine Ligands. ACS Catal. 2015, 5, 622.
ACKNOWLEDGMENTS
(
k) Ogawa, T.; Ruddy, A. J.; Sydora, O. L.; Stradiotto, M.; Turculet, L.
Cobalt- and Iron-Catalyzed Isomerization–Hydroboration of Branched
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New catalytic, oxidative dehydrosilylation:
R
CsF; BQ, Pd dba3
2
R
[
Si]
Application to olefin isomerization:
[
O]
R
[PdII]
[
Pt]
R
[Si]
F-
II
new catalytic [Pd H]
oxidative
H[Si] hydrosilylation
·
dual catalysis
dehydrosilylation
· net uphill reaction
new dehydrosilylation
rare alkylsilane activation
R
·
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[PdII]
·
R
·
translocation over 7 carbons
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