Hydrogen/deuterium exchange reactions of olefins with deuterium oxide mediated by the carbonylchlorohydridotris(triphenylphosphine)ruthenium(II) complex

Article abstract of DOI:10.1002/adsc.201000037

The catalytic properties of several ruthenium, osmium and rhodium hydride complexes for hydrogen/deuterium (H/D) exchange between olefins and deuterium oxide (D₂O) were investigated. The most effective catalytic precursor was found to be the carbonylchlorohydridotris(triphenylphosphine)ruthenium(II) complex. Through H/D exchange between metal hydride and D₂O, and reversible olefin insertion into an Ru-H(D) bond, protons attached to olefinic carbons and alkyl chains of olefins can all undergo H/D exchange with D ₂O. The catalytic reactions can be used to deuterate both terminal and internal olefins, for example, styrene, stilbene and cyclooctene.

Full text of DOI:10.1002/adsc.201000037

FULL PAPERS
DOI: 10.1002/adsc.201000037
Hydrogen/Deuterium Exchange Reactions of Olefins with
Deuterium Oxide Mediated by the Carbonylchlorohydrido-
tris(triphenylphosphine)ruthenium(II) Complex
Sunny Kai San Tse,a Peng Xue,a Zhenyang Lin,a,* and Guochen Jiaa,*
a
Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong
Kong, Peopleꢀs Republic of China
Fax : (+852)-2358-1594; phone: (+852)-2358-7361 or (+852)-2358-7379; e-mail: chjiag@ust.hk or chzlin@ust.hk
Received: January 15, 2010; Revised: April 18, 2010; Published online: May 28, 2010
Abstract: The catalytic properties of several rutheni- to olefinic carbons and alkyl chains of olefins can all
um, osmium and rhodium hydride complexes for hy- undergo H/D exchange with D2O. The catalytic reac-
drogen/deuterium (H/D) exchange between olefins tions can be used to deuterate both terminal and in-
and deuterium oxide (D2O) were investigated. The ternal olefins, for example, styrene, stilbene and cy-
most effective catalytic precursor was found to be clooctene.
the carbonylchlorohydridotris(triphenylphosphine)-
ACHTUNGTRENNUNGruthenium(II) complex. Through H/D exchange be-
tween metal hydride and D2O, and reversible olefin Keywords: alkenes; hydrides; isotopes; osmium;
À
insertion into an Ru H(D) bond, protons attached ruthenium
Introduction
eral H/D exchange reactions involving olefins and
deuterated organic solvents have been reported,[13] it
Deuterium labeled compounds are useful for a wide is surprising to note that much less work has been car-
range of applications. For example, they can be used ried out on direct catalytic H/D exchange between
as deuterated solvents, regents for mechanistic stud- olefins and D2O, even compared with reactions in-
ies, labeled drugs, and starting materials for deuterat- volving saturated hydrocarbons and D2O. The high
ed polymers. As a result, there has been much interest temperature-dilute acid method has been explored in
in developing effective methodology to synthesize the 1980s for the H/D exchange between D2O and
such compounds.[1] Transition metal-catalyzed direct olefins.[14] However, the method suffers from side re-
H/D exchange between organic compounds and ap- actions of skeletal rearrangements, or polymerization
propriate deuterium sources, being a very attractive and oligomerization of olefins.
approach to deuterated compounds, has been actively
There are only scattered reports of transition
explored by various researchers. In the past, many metal-mediated H/D exchange reactions between ole-
transition metal-catalyzed H/D exchange reactions of fins and D2O. In the area of heterogeneous catalysis,
[2]
organic substrates with D2 and deuterated organic it has been reported that perdeuterated cyclic olefins
solvents such as benzene, acetone and alcohols[3] have such as cyclohexene and cyclooctene could be ob-
been reported. Although D2O is the cheapest source tained by Pd/C-catalyzed H/D exchange with D2O at
of deuterium, it has been less used previously in elevated temperature (>1408C),[15] or under hydro-
metal-catalyzed H/D exchange reactions. The situa- thermal conditions (2508C/5 MPa).[16] In the area of
tion, however, is changing, as several systems have homogeneous catalysis, Fels et al. showed that a,b-un-
been found in recent years to catalyze the H/D ex- saturated carboxylic acid derivatives can undergo H/
change between D2O and organic substrates[4–12] in- D exchange reactions at the b-position with D2O in
cluding aromatics, saturated hydrocarbons and alco- the presence of Ir
hols.
ACHTUGTNREN(UNG COD)ACHUTNTGREN(NUGN acac) (2 mmol%, 908C),
presumably through cyclometallated intermediates.[17]
This work concerns H/D exchange between olefins Matsubara et al. demonstrated that cyclic olefins such
and D2O. Deuteration of olefins is interesting, be- as cyclohexene and cyclodecene can undergo H/D ex-
cause many readily available compounds contain a change with D2O under irradiation of microwaves in
C=C double bond and because olefins are useful start- the presence of RuCl
2ACHTUNGTREN(UNGN PPh3)3 (5 mol%, 1408C,
ing materials for making other compounds. While sev- 0.34 MPa).[18] Morrill et al. observed that partial deut-
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Hydrogen/Deuterium Exchange Reactions of Olefins with Deuterium Oxide
eration of octene, cyclohexene, and styrene occurred metal hydride complexes such as RuHCl(CO)ACHTUNGTRENNUNG(PPh3)3
when the substrates were treated with D2O in the (1), OsHCl(CO)
ACHTUGTNREN(NUG PPh3)3 (2), RuHClACHTUNGTERN(NUGN PPh3)3 (3) and
presence of RhCl3/BH3.[19] Milstein et al. reported RhH(CO)
AHCTUNGTRENNUNG
that the H/D exchange between D2O and terminal strated that RuHCl(CO)ACHTNUGTRNEGNU(PPh3)3 (1) can undergo in-
olefins such as styrene and tert-butylethylene can be sertion reactions with alkynes,[27,28] allenes[29] and func-
achieved with the cyclometallated rhodium complex tionalized olefins such as 2-vinylipyridine, and allylic
{[(t-Bu)2PCH2C6H4]RhH
60 for styrene).[20] Very recently, Grotjahn et al. de- (3),[31,32] OsHCl(CO)
scribed H/D exchange of D2O and a series of olefins
(solv)3}+ (608C, 24 h, TON= amines.[30] Insertion reactions of RuHCl
ACHUTGTNRENNUG ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
catalyzed by a [CpRu] complex.[21] Despite the im- been reported. In view of the reported reactivity
pressive progress, searching for catalytic systems that toward unsaturated substrates, one might expect that
can efficiently catalyze the H/D exchange reactions of these hydride complexes may undergo reversible in-
olefins with D2O under mild conditions for a wide sertion reactions with olefins and are potential candi-
range of olefin substrates is still desirable. In this dates for catalyzing H/D exchange between olefins
work, we wish to report that H/D exchange reactions and D2O, if they can undergo H/D exchange reactions
between D2O and olefins can be mediated by the air- with D2O.
stable, readily available ruthenium hydride complex
RuHCl(CO)(PPh3)3.
It was found experimentally that ca. 63% of the hy-
dride of RuHCl(CO)(PPh3)3 (1) was replaced with
N
ACHTUNGTRENNUNG
deuterium, after a mixture of 1 and D2O in a molar
ratio of 1:55 was heated at 1008C in THF for one
hour [Eq. (1)]. Under similar conditions, ca. 41% of
Results and Discussion
the hydride of OsHCl(CO)
with deuterium [Eq. (2)]. RuHCl
dergoes an H/D exchange reaction with D2O. In this
ACHTUNGTRENNUNG
Selection of Catalysts
ACHTUNGTRENNUNG
Previous studies on the chemistry of hydride and di- case, incorporation of deuterium into both hydride
hydrogen complexes have demonstrated that certain and the phenyl group of PPh3 occurred as determined
2
hydride complexes can undergo H/D exchange with by D NMR. Thus, the content of deuteration at the
D2O[22] or deuterated alcohols[23] to give deuteride hydride site cannot be accurately determined. We
complexes. In many cases, the H/D exchange reac- have also carried out H/D exchange reactions be-
tions could proceed through dihydrogen complexes[24] tween the hydride complex RhH(CO)
ACHTUNTRGNEUNG(PPh3)3 (4) and
or dihydrogen-bonded species.[25] Insertion of olefin D2O. Unfortunately, the extent of H/D exchange
into a metal-hydride bond and the reverse reaction could not be accurately determined because the com-
(b-H elimination) are well known organometallic re- plex partially decomposed to triphenylphosphine
actions.[26] We thus envisioned that H/D exchange be- oxide and some unidentified species during the ex-
tween olefins and D2O could proceed through H/D periment.
exchange between a metal hydride and D2O and re-
versible olefin insertion into an M H(D) bond, as il- 18e complexes MHCl(CO)
lustrated in Scheme 1.
The H/D exchange reactions of the six-coordinate
(PPh3)3 (M=Ru, Os) prob-
ably involve dihydrogen (B) or dihydrogen bonded
À
N
As the first step to explore the possibility of using species (A or A’) illustrated in [Eq. (3), as was pro-
well defined hydride complexes as catalysts to medi- posed previously for other related systems.[37] The hy-
ate H/D exchange between olefins and D2O, we have dride in RuHClACHTNUTGRNEUNG(PPh3)3 could be similarly deuterated.
first studied the H/D exchange reactions of D2O with
The catalytic properties of the hydride complexes
for H/D exchange between D2O and olefins were
then investigated using styrene as the model substrate.
The results are summarized in Table 1. When a 0.5M
solution of styrene was heated at 1008C with D2O
(13.5 molar equiv.) in 2 mL dioxane for 1 h in the
1
presence of RuHCl(CO)
N
2D NMR data indicate that ca. 85% of the olefinic
protons were replaced with deuterium while no deut-
eration occurred for the phenyl ring. The percentage
of deuterium incorporated into the styrene is essen-
tially equal to the statistical percentage of deuterium
on O of the heavy water and the vinyl carbons of sty-
rene, indicating that complete scrambling of deuteri-
um and hydrogen on O and vinyl C sites has been at-
tained (entry 1, Table 1). Styrene with over 95% deu-
Scheme 1.
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terium incorporation can be obtained if the exchange
reaction was repeated twice.
Table 1. Selection of catalysts for H/D exchange reactions of
olefins with D2O.[a]
The hydride complex OsHCl(CO)ACHTNUTRGNE(UNG PPh3)3 (2) was
also found to be active for the reaction, but the cata-
lytic reaction proceeds much more slowly (entries 4
and 5). RuHCl
(entry 3) and RhH(CO)
rather inactive. The poorer activity of RuHCl
(3) and RhH(CO)(PPh3)3 (4) could be related to their
G
ACHTUNGTERN(NUNG PPh3)3 (3)
AHCTUNGTRENNUNG
Entry Catalyst
%Dtheo. Time
[h]
%Dexp.
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
side reactions during H/D exchange reactions with
D2O. In the case of 3, the aryl groups of the phos-
phine ligands also undergo the H/D exchange. For 4,
decomposition of the complex was observed. Further
RuHCl(CO)ACTHUNTRGNEUNG(PPh3)3
(1)
1
2
3
4
5
90.0
89.9
90.1
89.9
90.6
90.3
1
study showed that RuHCl(CO)ACHTUNTRGNEUNG(PPh3)3 (1) is very effi-
RuHCl
N
4 .5
4.5
1
cient for the catalytic reaction and the reaction can be
accomplished even with 0.1 mol% of the catalyst. The
H/D reaction can be carried out in other solvents
such as dichloromethane, chloroform and THF.
RuHClACHTUNGTRENNUNG(PPh3)3 (3)
OsHCl(CO)ACHTUNGTRENNUNG(PPh3)3
(2)
Substrate Scope of the Catalytic Reactions
As shown in Table 2, RuHCl(CO)ACHTNUTRGEN(UNG PPh3)3 can also ef-
OsHCl(CO)ACHTUNGTRENNUNG(PPh3)3
(2)
fectively mediate the H/D exchange between D2O
and other terminal olefins that do not have a strong
coordinating group. With 3 mol% of the catalyst,
almost complete scrambling of deuterium and hydro-
gen on O and vinyl C sites is accomplished in 3.5 h.
However, the reaction involving 4-vinylpyridene gives
an unsatisfactory result, likely due to the competing
coordination of pyridine (entry 6).
The ruthenium complex 1 can also mediate the H/
D exchange between internal alkenes and D2O. Thus,
after a mixture of trans-stilbene and D2O in 1:9 molar
ratio was heated in the presence of 3 mol% of catalyst
1 at 1008C for 4.5 h, ca. 82.5% of the vinyl protons
were replaced with deuterium (theoretically, 90% of
4.5
4.5
RhH(CO)ACHTUNGTRENNUNG(PPh3)3
(4)
6
[a]
The H/D exchange reaction between styrene (1 mmol)
and D2O (99.9%) (13.56 mmol) was carried out in diox-
ane (2 mL) under N2 at 1008C in a Schlenk tube with
3 mol% of catalyst. %Dtheo. is the statistical percentage of
D when we consider the hydrogen atoms associated with
water and the vinyl group of styrene and the hydride of
the catalyst. %Dexp. is percentage of D determined exper-
imentally.
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Hydrogen/Deuterium Exchange Reactions of Olefins with Deuterium Oxide
Table 2. H/D exchange reactions of terminal alkenes with
D2O.[a]
Entry Sub/D2O/cat %Dtheo. Time
[h]
%Dexp.
1
2
1:13.52:0.03 90.00
3.5
3.5
1:18.0:0.03
90.00
Scheme 2.
change at a faster rate than the methyl protons. Thus,
in 1.5 h, H/D exchange mainly occurred for the vinyl
protons and ca. 88%, 87%, and 31.6% D were found
at the carbons of PhC, CMe and Me, respectively.
After the mixture had been heated for 10 h, ca. 88%,
87% and 77.3% D (theoretically, 89.9% of the vinyl
and methyl protons could be replaced with deuteri-
um) were found at the carbons of PhC, CMe and Me,
respectively [Eq. (4)].
We have tested the catalytic reaction using ethyl-
benzene as the substrate. Under similar reaction con-
ditions, ethylbenzene does not undergo the H/D ex-
change, indicating that the olefinic moiety is necessa-
ry.
3
4
5
1:13.52:0.03 90.01
1:13.50:0.03 90.00
1:13.59:0.03 90.05
1:13.56:0.029 90.03
3.5
3
19
69
6
Incorporation of deuterium in the vinyl positions is
expected to proceed through the general mechanism
shown in Scheme 1. The incorporation of deuterium
in the methyl group of PhCH=CHMe could occur by
two possible pathways. The first possibility involves
isomerization of PhCH=CHMe to PhCH2CH=CH2,
then H/D exchange with D2O for the olefinic protons,
and finally isomerization again as illustrated in
Scheme 3. The interconversion of PhCH=CHMe and
PhCH2CH=CH2 under the catalytic conditions is con-
sistent with the fact that PhCD=CDCD3 was also ob-
[a]
The reaction was carried out with 3 mol% of
RuHCl(CO)(PPh3)3 in dioxane (2 mL) under N2 at
ACHTUNGTRENNUNG
1008C in a Schlenk tube. %Dtheo. is the statistical percent-
age of D when we consider the hydrogen atoms associat-
ed with water and the vinyl group of styrene and the hy-
dride of the catalyst. %Dexp. is percentage of D deter-
mined experimentally. For entries 4 and 5, the reactions
were carried out in THF-d in an NMR tube.
the vinyl protons could be replaced with deuterium). tained in the deuteration experiment starting from
When cis-stilbene was subjected to the same reaction PhCH2CH=CH2. A control experiment shows that
conditions, deuterated trans-stilbene in which 82% of PhCH2CH=CH2 is completely converted to PhCH=
the vinyl protons were replaced with deuterium was CHMe when it was heated for 2.25 h in the presence
obtained, a result derived from isomerization as well of ca. 3 mol% of 1. Since PhCH=CHMe is more
as H/D exchange (Scheme 2).
stable than PhCH2CH=CH2, it is not surprising that
We have also studied H/D exchange reactions of the vinyl protons undergo H/D exchange at a faster
olefins having alkyl substituents. Heating a mixture of rate than those of the methyl group.
the internal olefin (Z)-PhCH=CHCH3 and D2O in a
Another possibility is that the deuterium is incorpo-
molar ratio of 1:22 in the presence of 1 resulted in in- rated into the methyl group of PhCH=CHMe by a
corporation of deuterium into both the vinyl and 1,2-deuterium shift as illustrated in Scheme 4 for the
methyl positions. The vinyl protons undergo H/D ex- conversion of PhCH=CDCH3 to PhCH=CHCH2D.
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Scheme 3.
Scheme 4.
The conversion occurs through a series of olefin inser-
tion and b-hydrogen elimination.
In a further experiment to demonstrate that pro-
tons of the alkyl carbon chain linked to a double
To demonstrate that the 1,2-deuterium shift mecha- bond can undergo H/D exchange with D2O, we have
nism is indeed possible, we have prepared partially studied H/D exchange reactions of PhCH=
deuterated b-methylstyrene by heating a mixture of CHCH2CH3.[39] It was found that complete deutera-
b-methylstyrene and D2O in the presence of 1 for a tion of the double bond as well as the side-chain can
short period of time (50 min). The sample of the par- also be achieved after
a
mixture of PhCH=
tially deuterated b-methylstyrene contains ca. 86% CHCH2CH3 and D2O was heated in the presence of
and 19.7% deuterium at the vinyl and methyl posi- 3 mol% of 1 for 10 h (Scheme 5).
tions, respectively. After the sample of the partially
As expected, the ruthenium hydride complex also
deuterated b-methyl styrene had been heated at catalyzed the H/D exchange between cyclooctene and
1008C in dioxane in the presence of catalyst 1 for 2 h, D2O to give per-deuterated cyclooctene. In-situ moni-
redistribution of deuterium among the vinyl and toring by NMR suggests that the H/D exchange rates
methyl group was observed, giving b-methylstyrene of the protons of vinyl group and the alkyl chain are
with the percentages of deuteration at vinyl and similar. When 1-hexene was used as the substrate, the
methyl group of 45%, 46% and 44.3%, respectively H/D exchange also occurred. Unfortunately, a compli-
[Eq. (5)].[38] The results suggest that the 1,2-deuterium cated mixture was produced due to the shift of the
shift mechanism shown in Scheme 4 can cause the double bond.
deuteration of the methyl group in b-methylstyrene.
We have also investigated ruthenium-catalyzed H/
D exchange reactions of the trisubstituted olefin
trans-a-methylstilbene (PhCMe=CHPh). After a mix-
ture of trans-a-methylstilbene and D2O in the pres-
ence of 3 mol% of 1 had been heated for 18 h, no H/
D exchange was observed. The lack of H/D exchange
between D2O and PhCMe=CHPh could be a result
related to the fact that the substrate does not undergo
insertion readily.
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Hydrogen/Deuterium Exchange Reactions of Olefins with Deuterium Oxide
Scheme 5.
Conclusions
was heated at 788C overnight. Water (15 mL) and diethyl
ether (15 mL) were added. The organic layer was separated
and the aqueous layer was further extracted with diethyl
ether (2ꢂ15 mL). The combined organic extract was washed
with a sodium metabisulfite solution and brine solution and
dried over MgSO4. The crude product was purified by
column chromatography using n-pentane as the eluent;
Yield: 0.514 g (69.1%). The NMR data suggest that the
product is a mixture of (Z)-PhCH=CHEt and (E)-PhCH=
CHEt in a ratio of 1:1.14 (based on integration of CH2
proton signals in the 1H NMR spectrum).
In summary, we have found that the readily available
hydride complex RuHCl(CO)ACHTUNTRGNEUNG(PPh3)3 can effectively
catalyze H/D exchange reactions of D2O with both
terminal and internal alkenes. Through H/D exchange
between metal hydride and D2O, and reversible olefin
À
insertion into a Ru D(H) bond, protons attached to
olefinic carbons and the alkyl chains of olefins can un-
dergo H/D exchange with D2O. The catalytic reac-
tions can be used to deuterate both terminal and in-
ternal olefins, for example, styrene, stilbene and cyclo-
octene.
Isomerization of (E)/(Z)-1-Phenylbut-1-ene to (E)-1-
Phenylbut-1-ene
Experimental Section
All manipulations were carried out at room temperature
under a nitrogen atmosphere using standard Schlenck tech-
niques unless otherwise stated. Solvents were distilled under
nitrogen from sodium benzophenone (hexane, ether, THF),
sodium (benzene), or calcium hydride (CH2Cl2). RhH(CO)-
[40]
[41]
[42]
G
RuHCl(CO)
E
RuHCl
E
and
A
mixture
3.29 mmol) prepared above and the ruthenium catalyst
RuHCl(CO)(PPh3)3 (97 mg, 0.102 mmol, 3.09 mol%) in
of
(E)/(Z)-1-phenylbut-1-ene
(0.435 g,
[43]
ACHTUNGTRENNUNG
ed procedures. 1,4-Dioxane was purged with nitrogen for
10 min before use. Deuterium oxide, 99.9 atom% D, was
purchased from Aldrich Chemical Co. and used as received.
All other reagents were used as purchased from Aldrich
Chemical Co., Acros Organics, International Laboratory
AHCTUNGTRENNUNG
THF (1 mL) was heated at 1008C for 45 min. The solvent
was removed under vacuum and the crude product was puri-
fied by column chromatography on silica gel using n-pen-
1
tane as the eluent; yield: 0.381 g (87.6%). The H NMR of
USA, or Kodak. H and 13C{1H} NMR spectra were collect-
1
the product indicates that it is mainly (E)-1-phenylbut-1-ene
[(E)-PhCH=CHEt, I (87.7%)] together with (Z)-1-phenyl-
but-1-ene [(Z)-PhCH=CHEt, I’ (4.4%)], (E)-PhCH2CH=
CHMe, II (6.1%) and (Z)-PhCH2CH=CHMe, II’ (1.8%).
1H NMR (400 MHz, CDCl3, 258C): d=7.36–7.17 (m, 5.5H,
Ph of I, I’, II, II’), 6.38 (d, J=15.6 Hz, 1H, Ph-CH=CH of I),
6.31–6.23 (dt, J=15.6, 6.4 Hz, 1H, CH=CH) 5.59–5.54 (m,
0.24H, CH=CH of I’, II, II’), 3.41 (d, J=5.2 Hz, 0.04H,
PhCH2 of II’), 3.32 (d, J=6.4 Hz, 0.14H, PhCH2 of II), 2.39–
2.31 (m, 0.1H, =CH-CH2-CH3 of I’), 2.27–2.20 (m, 2H,
=CHCH2CH3 of I), 1.72 (d, J=4.8 Hz, 0.06H, =CHCH3 of
II’), 1.68 (d, J=6 Hz, 0.21H, =CHCH3 of II), 1.11–1.07 (t,
J=7.6 Hz, 3H, CH2CH3 of I). The signal of the CH3 group
of I’ is merged with that of the CH3 of I.
ed on a Bruker ARX 300 MHz spectrometer or a Bruker
AV 400 MHz spectrometer. D NMR spectra were collected
on a Bruker AV 400 MHz spectrometer.
2
Synthesis of (E)/(Z)-1-Phenylbut-1-ene[44]
To a THF solution (5 mL) of propyltriphenylphosphonium
bromide (2.17 g, 5.63 mmol) cooled at 08C by an ice-bath
was slowly added a hexane solution of tert-butyllithium
(1.6M, 3.6 mL, 5.76 mmol). The orange mixture was stirred
at room temperature for 1 h. Then benzaldehyde (0.80 mL,
7.84 mmol) was added to the mixture to give a pale-yellow
solution with some white precipitate. The reaction mixture
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Isomerization of Allylbenzene
General Procedure of RuHCl(CO)ACTHUNGETRN(NUG PPh3)3-Catalyzed
H/D Exchange Reactions between Terminal Olefins
and D2O
A
mixture of allylbenzene (45 mL, 0.366 mmol) and
RuHCl(CO)(PPh3)3 (105 mg, 0.011 mmol, 3.01 mol%),
ACHTUNGTRENNUNG
water (150 mL) in degassed dioxane (3 mL) was heated at
1008C for 2.25 h. The product was extracted by diethyl ether
and dried over MgSO4. The crude product was then purified
by column chromatography using n-pentane as the eluent;
A mixture of RuHCl(CO)ACHTUNGTRENUNG(PPh3)3, olefin and D2O in diox-
ane (2 mL) in a stoppered Schlenck tube was stirred and
heated by an oil bath at 1008C for a given period of time.
The reaction mixture was cooled to room temperature and
then extracted with diethyl ether. The combined organic ex-
tract was washed with water and a brine solution and dried
over MgSO4. The crude product was purified by column
chromatography on silica gel using n-pentane as the eleunt.
1
yield: 19 mg (43%). The H NMR of the product is identical
to that of (E)-PhCH=CHMe. 1H NMR (300 MHz, CDCl3,
258C): d=7.36–7.19 (m, 5H, Ph), 6.43 (dd, J=16, 1.2 Hz,
1H, PhCH=), 6.29–6.24 (dq, J=15.6, 6.4 Hz, 1H, =CH-
Me), 1.92–1.90 (dd, J=6.4, 1.6 Hz, 3H, =CHMe).
Deuteration of Styrene
General Procedure of H/D Exchange Reactions
between Metal Hydride Complexes and D2O
A THF solution (2 mL) containing
a metal complex
(0.10 mmol) and D2O (100 mL, 5.6 mmol) in a stoppered
Schlenck tube was stirred and heated by an oil bath at
1008C for 1 h. The solvents were removed under vacuum,
the residue was washed with hexane (3 mL) and diethyl-
ether (2 mLꢂ2), then dried under vacuum to give the prod-
uct.
Styrene (115 mL, 1.00 mmol), RuHCl(CO)ACHTNURTGNEUNG(PPh3)3 (280 mg,
29.4 mmol, 2.94 mol%), D2O (242 mL, 13.5 mmol); reaction
time: 1 h; yield: 81.3 mg (75.9%). Theoretical percentage of
deuteration at the vinyl position=90.0%. 1H NMR
(400 MHz, CDCl3, 258C): d=7.42–7.26 (m, 5H, Ph), 6.71
(m, 0.15H, Ph-CHa=), 5.74 (m, 0.16H, =CHb), 5.23 (m,
0.16H, =CHc); 2D NMR (61.4 MHz, dichloromethane+
CDCl3, 258C): d=6.63 (s, Da), 5.66 (s, Db), 5.15 (s, Dc).
RuDCl(CO)
N
RuHCl(CO)
A
(95 mg,
0.10 mmol), D2O (0.10 mL, 5.6 mmol); yield: 79 mg (83%);
1
white solid. H NMR (400 MHz, CD2Cl2, 298 K): d=À7.24
(br d, J=82.8 Hz, 0.37H, RuH), 7.06–7.32 (m, 45H, Ph);
31P{1H} NMR (161.9 MHz, CD2Cl2, 298 K): d=12.16 (br s),
39.22 (br s); 2D NMR (61.42 MHz, CD2Cl2, 298 K): d=
À7.37 (br).
Deuteration of p-Methoxystyrene
OsDCl(CO)
N
OsHCl(CO)
A
(104 mg,
0.10 mmol), D2O (0.10 mL, 5.6 mmol); yield: 96 mg (92%);
1
white solid. H NMR (300 MHz, CD2Cl2, 298 K): d=À6.93
(dt, J=86.8, 24.4 Hz, 0.59H, OsH), 7.02–7.31 (m, 45H, Ph);
31P{1H} NMR (161.9 MHz, CD2Cl2, 298 K): d=7.12 (d, J=
11.9 Hz), À9.92 (t, J=11.9 Hz); 2D NMR (61.42 MHz,
CD2Cl2, 298 K): d=À7.05 (br).
p-Methoxystyrene
(97%,
66.5 mL,
0.485 mmol),
RuDClACHTUNGTRENNUNG(PPh3)3: RuHClCAHTUNGTREN(NNGU PPh3)3 (95 mg, 0.10 mmol), D2O
RuHCl(CO)(PPh3)3 (14.5 mg, 15.2 mmol, 3.13 mol%); D2O
AHCTUNGTRENNUNG
(0.10 mL, 5.6 mmol); yield: 72 mg (78%); purple solid.
1H NMR (300 MHz, CD2Cl2, 298 K): d=À18.23 (q, J=
26.4 Hz, 0.8H, RuH), 6.99–7.22 (m, 45H, Ph); 31P{1H} NMR
(161.9 MHz, CD2Cl2, 298 K): d=57.33 (br); 2D NMR
(61.42 MHz, CD2Cl2, 298 K): d=À18.11 (br, 1D), 7.24 (br,
23D), 7.69 (br, 7D).
(121 mL, 6.77 mmol), dioxane (1 mL); reaction time: 3.5 h;
yield: 50 mg (73%). Theoretical percentage of deuteration
at the vinyl position=90.3%. H NMR (400 MHz, acetone-
d6, 258C): d=7.53 (d, J=8.8 Hz, 2H), 7.04 (d, J=8.8 Hz,
2H), 6.81 (br, 0.16H, CHa=), 5.76 (br, 0.16H, =CHb), 5.21
(br, 0.16H, =CHc), 3.93 (s, 3H, OCH3); 2D NMR
(61.4 MHz, acetone+acetone-d6, 258C): d=6.83 (s, Da),
5.78 (s, Db), 5.23 (s, Dc).
1
General Procedure for Screen Test of Metal
Complexes for Catalytic H/D Exchange Peactions
between Styrene and D2O
Deuteration of 4-Vinylpyridine
A mixture of a catalyst (0.03 mmol), styrene (115 mL,
1.00 mmol) and D2O (242.5 mL, 13.56 mmol) in dioxane
(2 mL) in a stoppered Schlenck tube was stirred and heated
by an oil bath at 1008C for a given period of time. The reac-
tion mixture was extracted with diethyl ether. The combined
organic extract was washed with water and a brine solution
and dried over MgSO4. The crude product was purified by
column chromatography on silica gel using n-pentane as the
4-Vinylpyridine (108 mL, 1.00 mmol), RuHCl(CO)
(28.0 mg; 29.4 mmol, 2.91 mol%), D2O (242.5 mL,
13.57 mmol); reaction time: 69 h; yield: 64 mg (59%). Theo-
ACHTUNGTRENNUNG(PPh3)3
1
2
eluent. The product was characterized by H and D NMR.
retical percentage of deuteration at the vinyl position=
1
90.1%. H NMR (400 MHz, CDCl3, 258C): d=8.55 (d, J=
4.4 Hz, 2H, Py), 7.27 (d, J=5.6 Hz, 2H, Py), 6.65 (m,
0.70H, CHa=), 5.95 (m, 0.75H, =CHb), 5.46 (m, 0.66H,
1518
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Adv. Synth. Catal. 2010, 352, 1512 – 1522

Hydrogen/Deuterium Exchange Reactions of Olefins with Deuterium Oxide
=CHc); 2D NMR (61.2 MHz, dichloromethane+CDCl3,
258C): d=6.61 (s, Da), 5.93 (s, Db), 5.44 (s, Dc).
Deuteration of 2-Vinylnaphthalene
1H NMR (400 MHz, CDCl3, 258C): d=7.53–7.52 (m, 4H,
Ph), 7.39–7.35 (m, 4H, Ph), 7.29–7.25 (m, 2H, Ph), 7.11 (br,
2
s, 0.35H, CH=CH); D NMR (61.2 MHz, acetone-d6, 258C):
d=7.33 (br, s, CD=CD).
2-Vinylnaphthalene
(98%,
78.8 mg,
0.500 mmol),
Deuteration of cis-Stilbene
RuHCl(CO)(PPh3)3 (14.4 mg, 15.1 mmol, 3.02 mol%); D2O
ACHTUNGTRENNUNG
(121 mL, 6.77 mmol); reaction time: 3.5 h; yield: 61 mg
(77.6%). Theoretical percentage of deuteration at the vinyl
position=90.0%. 1H NMR (400 MHz, acetone-d6, 258C):
d=8.01 (m, 4H, naph), 7.87 (m, 1H, naph), 7.62 (m, 2H,
naph), 7.09 (br s, 0.11H, CHa=), 6.09 (m, 0.12H, CHc), 5.46
2
(m, 0.12H, =CHb); D NMR (61.4 MHz, acetone+acetone-
d, 258C): d=7.09 (s, Da), 6.10 (s, Dc), 5.48 (s, Db).
cis-Stilbene (97%, 184 mL, 1.00 mmol), RuHCl(CO)ACHTUNGTRENNUNG(PPh3)3
(28.6 mg; 30.0 mmol, 3 mol%), D2O (161 mL, 9.01 mmol); re-
action time: 4.5 h; yield: 134 mg (73.5%). cis-Stilbene was
isomerized to trans- stilbene in the reaction. Theoretical per-
centage of deuteration at the vinyl position=90.0%.
1H NMR (400 MHz, CDCl3, 258C): d=7.54–7.51 (m, 4H,
Ph), 7.4–7.34 (m, 4H, Ph), 7.27–7.25 (m, 2H, Ph), 7.11 (br s,
0.36H, CH=CH); 2D NMR (61.2 MHz, acetone-d6, 258C):
d=7.33 (br s, CD=CD).
Deuteration of Triethoxyvinylsilane
The reaction was performed in an NMR tube. Triethoxyvi-
nylsilane (97%, 55.5 mL 0.254 mmol), RuHCl(CO)ACHTNUTRGNE(UNG PPh3)3
Deuteration of trans-b-Methylstyrene
(7.3 mg, 7.66 mmol, 3.02 mol%), D2O (61.5 mL, 3.44 mmol);
THF-d (0.3 mL); reaction time: 3 h. Theoretical percentage
of deuteration at the vinyl position=90.0%. 1H NMR
(300 MHz, THF-d, 258C): d=6.01 (br, 0.31H, CH=CH2),
3.67–3.61 (q, J=7.02 Hz, 6H, OCH2CH3), 1.24–1.19 (t, J=
7.02 Hz, 9H, OCH2CH3); 2D NMR (61.4 MHz, THF-d,
258C): d=5.89 (br).
trans-b-Methylstyrene (130 mL, 1.00 mmol), RuHCl(CO)-
AHCTUNGTERN(GNUN PPh3)3 (29.0 mg, 30.4 mmol, 3.04 mol%), D2O (402 mL,
22.5 mmol); reaction time: 10 h; yield: 98 mg (81.5%). The-
oretical percentage of deuteration at the vinyl and alkyl po-
sition=90.0%. H NMR (300 MHz, CDCl3, 258C): d=7.39–
Deuteration of Ethyl Acrylate
1
7.30 (m, 4H, Ph), 7.25–7.19 (m, 1H, Ph), 6.44 (br, 0.126H,
PhCHa), 6.26 (br, 0.12H, =CHb), 1.88 (br, 0.404H, CHD2);
2D NMR (61.2 MHz, dichloromethane+CDCl3, 258C): d=
6.38 (s, 1D, Da), 6.23 (s, 1D, Db), 1.79 (s, 2.99D, CD3).
Deuteration of b-Ethylstyrene
The reaction was performed in an NMR tube. Ethyl acrylate
(99%, 25 mL, 0.228 mmol), RuHCl(CO)ACHTNURTGNE(UNG PPh3)3 (6.6 mg,
6.93 mmol, 3.04 mol%), D2O (55.5 mL, 3.11 mmol), THF-d
(0.3 mL); reaction time: 16.5 h. Theoretical percentage of
deuteration at the vinyl position=90.1%. 1H NMR
(400 MHz, THF-d, 258C): d=6.39 (br, 0.15H, =CHb), 6.17
(br, 0.1H, CHa=), 5.91 (br, 0.15H, =CHc), 4.23 (q, J=
7.2 Hz, 2H, OCH2CH3), 1.32 (t, J=7.2 Hz, 3H, CH2CH3);
2D NMR (61.4 MHz, THF-d, 258C): d=6.24 (s, Db), 6.03 (s,
Da), 5.77 (s, Dc).
b-Ethylstyrene (133 mg, 1.01 mmol), RuHCl(CO)ACHTUNGTRENNUNG(PPh3)3
(28 mg, 29.39 mmol, 2.91 mol%), D2O (563 mL, 31.5 mmol);
reaction time: 10 h; yield: 116 mg (83.3%). Theoretical per-
centage of deuteration at the vinyl and alkyl positions=
Deuteration of trans-Stilbene
1
90.0%. H NMR (400 MHz, acetone-d, 258C): d=7.34–7.19
(m, 5H, Ph), 6.38 (br, 0.125H, PhCHa=), 6.31 (br, 0.125H,
=CHb), 2.16 [br, 0.24H, CH(D)], 1.01 (br, 0.4H, CHD2);
2D NMR (61.2 MHz, acetone+CDCl3, 258C): d=6.25 (br,
2D, Da and Db), 2.23 (br, 2D, CD2), 0.97 (br, 3D, CD3).
trans-Stilbene (180 mg, 0.998 mmol), RuHCl(CO)ACHTNUGTRNEG(UN PPh3)3
(29.0 mg, 30.4 mmol, 3.05 mol%), D2O (161 mL, 9.01 mmol);
reaction time: 4.5 h; yield: 154 mg (84.5%). Theoretical per-
centage of deuteration at the vinyl position=90.1%.
Adv. Synth. Catal. 2010, 352, 1512 – 1522
ꢁ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
1519

Sunny Kai San Tse et al.
FULL PAPERS
Deuteration of 4-Vinylbenzoic Acid
Acknowledgements
This work was supported by the Hong Kong Research Grant
Council (Project Nos. HKUST 601306 and HKUST 602108).
References
4-Vinylbenzoic
acid
(97%,
76.4 mg,
0.500 mmol),
RuHCl(CO)(PPh3)3 (14.4 mg, 15.1 mmol, 3.02 mol%), D2O
ACHTUNGTRENNUNG
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(161 mL, 9.01 mmol), dioxane (1 mL); reaction time: 3.5 h.
After the reaction, the product was extracted with chloro-
form. The combined organic extract was dried over MgSO4.
After removal of the solvent, the solid was re-dissolved in
ethanol and filtered to remove the catalyst. The solvent of
filtration was removed to obtain the final product; yield:
66.6 mg (90%). Theoretical percentage of deuteration at the
vinyl position=90.0%. 1H NMR (400 MHz, acetone-d6,
258C): d=8.16 (d, J=8.4 Hz, 2H), 7.73 (d, J=8.4 Hz, 2H),
6.96 (br, 0.15H, =CHa), 6.08 (br, 0.14H, =CHc), 5.52 (br,
0.12H, =CHb); 2D NMR (61.4 MHz, acetone+acetone-d6,
258C): d=6.99 (s, Da), 6.11 (s, Dc), 5.54 (s, Db).
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Deuteration of Cyclooctene
The H/D exchange experiment was carried out in 2 steps.
1st step: cyclooctene (1.10 mL, 8.44 mmol), RuHCl(CO)-
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
(333 mg, 350 mmol, 4.1 mol%), D2O (4.30 mL, 240.4 mmol);
reaction time: 44 h; overall yield: 360 mg (39%). Theoretical
percentage of deuteration at the vinyl and alkyl positions
cannot be determined since the reaction proceeds via two
steps. 1H NMR (400 MHz, CDCl3, 258C): d=5.61 (s, 2H,
CH=), 2.09 (s, 3.72H, =CDCHD), 1.43 (s, 7.70H, other
CHD); 13C{1H} NMR (100.6 MHz, CDCl3, 258C): d=129.89
(residual =CH), 129.56 (t, J=23.14 Hz, =CD of deuterated
COE), 28.2 (m, CD2 of deuterated COE), 24.86 (m, CD2 of
deuterated COE). Normal 13C{1H} NMR integration cannot
be used for quantitative analysis. In this work, the intensities
of the 13C signals of =CH and =CD have been determined
by inverse gated decoupling 13C{1H} NMR. The relaxation
time d1 is set to 12 sec and the number of scans is 4116.
Based on the =CH/=CD intensity ratio of 0.52:3.04, it was
estimated that the vinyl carbon has ca. 85.4% of deuterium.
2D NMR (61.25 MHz, CH2Cl2, 258C): d=5.59 (s, 1D), 2.03
(s, 2D), 1.38 (s, 4D).
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Attempted Deuteration of trans-a-Methylstyrene
trans-a-Methylstyrene
(99%,
195 mg,
0.994 mmol),
RuHCl(CO)(PPh3)3 (28.5 mg, 29.9 mmol, 3.01 mol%), D2O
G
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(m, 10H, Ph), 6.84 (s, 1H, =CH), 2.29 (s, 3H, PhCMe=).
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