New chiral rhenium complexes of unsaturated alcohols: Preparation and reactivity

Article abstract of DOI:10.1016/S0022-328X(98)00670-6

New chiral rhenium complexes of allylic, homoallylic and propargylic alcohols have been prepared and their reactivity versus various reagents has been studied. Starting from the allyl alcohol complex, a multistep sequence involving a chemoselective oxidation, a Wittig reaction and a reduction led without bond-shift to conjugated dienone and dienol. The complexed allyl acetate, prepared by reaction of acetic anhydride on the complexed allyl alcohol reacted with sodium dimethylmalonate in a diastereoselective fashion.

Full text of DOI:10.1016/S0022-328X(98)00670-6

Journal of Organometallic Chemistry 567 (1998) 75–81
New chiral rhenium complexes of unsaturated alcohols: preparation
and reactivity
Ste´phanie Legoupy, Christophe Cre´visy, Jean-Claude Guillemin *, Rene´ Gre´e
Laboratoire de Synthe`ses et Acti6ations de Biomole´cules, ESA CNRS 6052, ENSCR, 35700 Rennes, France
Received 7 October 1997; received in revised form 8 December 1997
Abstract
New chiral rhenium complexes of allylic, homoallylic and propargylic alcohols have been prepared and their reactivity versus
various reagents has been studied. Starting from the allyl alcohol complex, a multistep sequence involving a chemoselective
oxidation, a Wittig reaction and a reduction led without bond-shift to conjugated dienone and dienol. The complexed allyl acetate,
prepared by reaction of acetic anhydride on the complexed allyl alcohol reacted with sodium dimethylmalonate in a diastereose-
lective fashion. © 1998 Elsevier Science S.A. All rights reserved.
Keywords: Chiral rhenium complexes; Oxidation; Reduction; Wittig reaction; Diastereoselectivity
1. Introduction
derivatives is however a serious limitation to their use
in synthetic chemistry. Among all these complexes,
none are able to associate a chiral center at the metallic
atom along with a good chemical stability, a combina-
tion which would be of great versatility in organic and
asymmetric synthesis. Gladysz et al. [6] have prepared
chiral rhenium derivatives and the compound [(p5-
C5H5)Re(NO)(PPh3)(CH3)] 1 has been used to complex
alkenes and alkynes [7]. The corresponding rhenium
salt could act as a protecting group for a double or a
triple bond, activate a bonded substrate or be useful in
enantioselective transformations (Scheme 1).
The complexation of carbon-carbon double or triple
bonds by transition metals has been extensively studied
[1]. For instance, complexes of alkynyl compounds are
efficiently prepared starting from dicobalt octacarbonyl
[2]. Such complexes are very stable and therefore are of
much use in organic synthesis. However, they do not
have stable chiral centers at the metallic atoms, a
limiting factor for their application in asymmetric syn-
thesis. Within the alkenyl complexes family, the iron,
osmium and manganese carbonyl derivatives have been
studied in more details with regard to their synthetic
potentialities. Rosemblum et al. [3] have complexed
alkenes with CpFe(CO)2 and obtained good results in
reactions with various nucleophiles. Some osmium
complexes are able to promote electrophilic addition
reactions on p2-bound arene [4] but questions remain
about their potential toxicity. Interesting applications
of manganese complexes in stereoselective alkylations
have been recently reported [5]; the instability of such
* Corresponding author. Tel.: +33 2 99871387; fax: +33 2
99871384; e-mail: jean-claude.guillemin@ensc-rennes1.fr
Scheme 1.
0022-328X/98/$19.00 © 1998 Elsevier Science S.A. All rights reserved.
PII S0022-328X(98)00670-6

76
S. Legoupy et al. / Journal of Organometallic Chemistry 567 (1998) 75–81
reported for other unsaturated derivatives of rhenium
1
complexes [7]. Diastereomers were observed in the H
and 13C-NMR spectra of the 3-butyn-2-ol 5b (ratio:
55:45) and 3-buten-1-ol complexes 6b (ratio: 84:16). The
presence of the two rotamers of 2-butyn-1-ol 5c, in a
50:50 ratio, has also been clearly evidenced.
The chemoselective oxidation of these complexes was
first investigated using compounds 5b,c, 6a; their reac-
tion with manganese dioxide or pyridinium chlorochro-
mate (PCC) was not successful while only partial
reaction was observed using TEMPO (2,2,6,6-te-
tramethyl-1-piperidinyloxy). Iodoxybenzoic acid (IBX)
[10] was found to be a very efficient and mild reagent in
these transformations. Compounds 7b,c, 8a were ob-
tained in 76, 65 and 61% yields, respectively (Scheme
3). Aldehyde 7c was obtained as a mixture of two
rotamers in a 3:2 ratio. The y-acrolein complex 8a
prepared by the oxidation of 6a is identical (with a
similar 60:1 ratio of diastereomers) to the derivative
obtained by direct complexation of acrolein with 2 [11].
The formation of a conjugated dienic compound,
selectively complexed at only one carbon-carbon multi-
ple bond has been achieved starting from the acrolein
Scheme 2.
We report here the preparation of new chiral rhe-
nium complexes of propargylic, allylic and homoallylic
alcohols. We show on several examples the compatibil-
ity of such complexes with various organic reactions: a
chemoselective oxidation of some of these complexed
alcohols, a Wittig reaction on the complexed acrolein
and a chemoselective reduction of the formed dienone
complex. All these reactions occur without bond-shift.
Also described is the preparation of complexed allyl
acetate by addition of acetic anhydride on the com-
plexed allyl alcohol and its diastereoselective reaction
with sodium dimethylmalonate. A portion of this work
has been communicated in a preliminary form [8].
complex 8a.
A
Wittig reaction using methyl
(triphenylphosphoranylidene)ketone in CH3CN at 65°C
led to the dienone 9, purified by precipitation (CH2Cl2/
EtOH) and isolated in a 73% yield (Scheme 4). The
chemoselective reduction of the formed compound 9
using NaBH4 in CH3OH gave the alcohol 10 in a 69%
yield. Due to the presence of a newly created stereo-
genic center, a 55:45 mixture of two diastereoisomers
was observed. In both reactions no bond-shift was
observed, and this is an important result with regard to
the possible use of such complexes as selective chiral
protecting groups for one double bond in a conjugated
polyenic system.
2. Results and discussion
The
labile
dichloromethane
complex
[(p5-
C5H5)Re(NO)(PPh3)(CH2Cl2)]+BF4− 2, easily formed
at −78°C from the methyl complex 1 [9], reacts with
propargylic 3a–d, allylic 4a and homoallylic alcohols 4b
to give the corresponding adducts 5a–d and 6a,b
(Scheme 2). Yields range from 54 (5d) to 81% (5c). Such
compounds are easily chromatographed or purified by
precipitation.
Complexes 5a–d, 6a,b have been characterized by
1
infrared, H, 31P and 13C-NMR spectroscopy and high
resolution mass spectrometry (HRMS). The 1H and
13C-NMR signals of the complexed CꢀC atoms of
compounds 5a–d were shifted down-field to those of
the corresponding atoms in the free alcohols while the
1H and 13C-NMR signals of the complexed CꢁC atoms
of compounds 6a,b were shifted up-field. These chemi-
cal shifts are in good agreement with those already
Scheme 3.

S. Legoupy et al. / Journal of Organometallic Chemistry 567 (1998) 75–81
77
Scheme 4.
We have recently reported regioselective substitutions
of rhenium complexes of allylic alcohols under acidic
conditions [12]. It was of interest to study also the
possibility of nucleophilic substitution under basic con-
ditions starting from the allylic acetate complex. How-
ever since direct additions of nucleophiles on rhenium
complexes of alkenes have been reported [11], the com-
petition between the two processes (addition or substi-
tution) had to be studied. The acetate complex 11 was
formed in a very low yield by direct complexation.
Better results (70% yield) were obtained by reaction of
6a with acetic anhydride in the presence of pyridine.
The reaction of complex 11 with sodium malonate,
prepared in situ from NaH and dimethylmalonate, led
in a 69% yield to a neutral complex 12 easily identified
from the spectral and analytical data (Scheme 5).
of these complexes in such reactions as nucleophilic or
electrophilic additions and cycloadditions as well as
extension to asymmetric synthesis (the complex 1 has
been resolved) [6] are currently under progress.
4. Experimental section
4.1. General
All manipulations were performed under nitrogen
atmosphere. Dichloromethane was distilled from P4O10.
HBF4 ·Et2O was purchased from Aldrich and used as
received. All other starting materials were obtained
commercially and used as such or purified by standard
means.
Proton and carbon magnetic resonance spectra were
taken on a Bruker AC 400 spectrometer, and the
chemical shifts are reported on the scale l relative to
tetramethylsilane (1H) or to solvent (13C, l=77.7/
CDCl3, l=62.8/CD3NO2). High resolution mass spec-
tra were recorded on an MS/MS ZabSpec TOF VG
Analytical spectrometer at a FAB positive ionisation
with Cs+ by the CRMPO (Centre Regional de Mesures
Physiques de l’Ouest).
1
Furthermore, the H and 13C-NMR spectra clearly
show that only one diastereomer has been formed: the
signal of the methylene connected to the rhenium atom
2
presents a doublet with a coupling constant JCP=5.3
Hz while a signal with a smaller coupling constant
3JCP=4.2 Hz was observed for the CH group in i-po-
sition. By analogy with the reported reaction of
cuprates with complexed monosubstituted alkenes [13],
the attack of sodium dimethylmalonate is probably
performed at the less substituted olefinic carbon and on
the CꢁC face anti to the rhenium. No substitution
product has been detected in this reaction.
4.1.1. General procedure for preparation of propargylic
5a–d and homoallylic alcohol complexes 6b.
A sample of complex (p5-C5H5)Re(NO)(CH3)(PPh3)
1 (100 mg, 0.179 mmol) and CH2Cl2 (10 ml) were
cooled to −78°C and HBF4 ·OEt2 (85%, 32 ml, 0.185
mmol) was added with stirring. After 30 min, a large
excess of alcohol (2 ml) was added. The reaction mix-
ture was allowed to warm to room temperature (r.t.)
and stirred overnight. Solvent was removed by rotary
evaporation. The resulting residue was chro-
matographed on a silica gel column with use of 4:1
3. Conclusion
We have shown that propargylic, allylic and homoal-
lylic alcohols can be easily complexed with rhenium
complex 2. Using carefully selected reagents, chemose-
lective oxidation, reduction or a Wittig reaction can be
performed on these complexes. Studies of the reactivity

78
S. Legoupy et al. / Journal of Organometallic Chemistry 567 (1998) 75–81
Scheme 5.
dichloromethane/acetone (v/v) to give compound 5a–d
or 6b as a yellow-brown oil.
MHz, CD3COCD3) l: 134.3 (JCP=10.7, o–Ph); 133.3
(JCP=2.7, p–Ph); 130.6 (JCP=10.7, m–Ph); 100.2
(C5H5); 110.8 (C6 ꢀCH); 79.2 (JCP=14.1, CꢀC6 H); 69.5
4.1.2. [(p5-C5H5)Re(NO)(PPh3)(HCꢀCCH2OH)]+
[BF4]− 5a
(CHOH); 24.3 (CH3). 31P {1H}-NMR (121 MHz,
CD3COCD3) l: 17.6 (s). IR (cm−1, neat): wNO 1703
2-Propynol was used as alcohol. Yield: 72.8 mg,
0.106 mmol, 59%. 1H-NMR (CD3COCD3, 400 MHz) l:
7.60–7.74 (m, 9H, PPh3); 7.44–7.58 (m, 6H, PPh3); 6.80
(vs);
wCꢀC
(C27H26NO2PRe)+: 614.1276; found: 614.1267.
1799
(m).
HRMS:
calc.
for
(dt, 1H, J=1.5, JPH=19.3, ꢀCH
5.25 (m, 1H, CH2OH); 5.11 (m, 1H, CH2
1H, J=5.6, CH2OH
). 13C-NMR (CD3COCD3, 100
MHz) l: 134.4 (JCP=10.3, o–Ph); 133.3 (JCP=2.7,
p-Ph); 130.6 (JCP=11.4, m–Ph); 107.0 (s, –CꢀCH);
H); 61.8
6
); 6.24 (s, 5H, C5H5);
4.1.4. [(p5-C5H5)Re(NO)(PPh3)(H3CCꢀCCH2OH)]+
[BF4]− 5c
2-Butyn-1-ol was used as alcohol. Yield: 102 mg,
0.145 mmol, 81%. Two rotamers 50:50. H-NMR (400
MHz, DMSO) l: 7.46–7.85 (m, 24H, PPh3); 7.14–7.35
(m, 6H, PPh3); 6.20 (s, 10H, C5H5); 5.83 (t, 1H, J=6.1,
6
6
OH); 5.02 (t,
6
1
6
100.1 (C5H5); 79.7 (JCP=14.1, –CꢀC
6
(CH2OH). 31P {1H} NMR (CD3COCD3, 121 MHz) l:
17.9 (s). IR (cm−1, neat) wNO 1704 (vs), wCꢀC 1797.
HRMS calc. for C26H24NO2PRe: 600.1103, found:
600.1101.
CH2OH
J=16.3, 5.1, CH2
CH2OH); 3.74 (dd, 1H, J=16.3, 6.1, CH2
(dd, 1H, J=16.3, 6.1, CH
6
); 5.54 (t, 1H, J=5.1, CH2OH
OH); 4.86 (dd, 1H, J=16.3, 5.1,
OH); 3.55
2OH); 3.06 (s, 3H, CH3); 1.84
6 ); 5.14 (dd, 1H,
6
6
6
6
(s, 3H, CH3). 13C-NMR (100 MHz, DMSO) l: 126.0–
135.0 (Ph); 105.5 (CꢀC); 99.8 (C5H5); 99.1 (C5H5); 98.2
(CꢀC); 85.8 (JCP=12.2, CꢀC); 84.8 (JCP=13.3, CꢀC);
4.1.3. [(p5-C5H5)Re(NO)(PPh3)(HCꢀCCH(CH3)OH)]+
[BF4]-− 5b
3-Butyn-2-ol was used as alcohol. Yield: 86.9 mg,
0.124 mmol, 69%. Two diastereomers 45:55 (minor).
1H-NMR (400 MHz, CD3COCD3) l: 7.59–7.75 (m,
9H, PPh3); 7.43–7.57 (m, 6H, PPh3); 6.77 (dd, 1H,
61.7 (CH2OH); 60.8 (JCP=6.1, CH2OH); 18.2 (JCP=
1.9, CH3); 12.1 (JCP=5.7, CH3). 31P {1H}-NMR (121
MHz, DMSO) l: 13.0 (s); 16.9 (s). IR (cm−1, neat):
wNO 1702 (vs); wCꢀC 1880 (m). HRMS: calc. for
(C27H26NO2PRe)+: 614.1276; found: 614.1260.
J
PH=19.3, J=1.5, ꢀCH); 6.26 (s, 5H, C5H5); 5.66–
5.77 (m, 1H, CHOH); 5.07–5.16 (m, 1H, CHOH); 1.57
(d, 3H, J=6.1, CH3). 13C-NMR (100 MHz,
CD3COCD3) l: 134.3 (JCP=10.7, o–Ph); 133.3 (JCP
2.7, p–Ph); 130.6 (JCP=10.7, m–Ph); 111.1 (CꢀCH);
6
6
4.1.5.
=
[(p5-C5H5)Re(NO)(PPh3)(HOCH2CꢀCCH2OH)]+
6
[BF4]− 5d
99.9 (C5H5); 78.9 (JCP=14.1, CꢀC
6
H); 65.2 (CHOH);
2-Butyn-1,4-diol was used as alcohol. Yield: 69.5 mg,
0.097 mmol, 54%. H-NMR (400 MHz, CD3COCD3)
l: 7.58–7.83 (m, 11H, PPh3); 7.27–7.45 (m, 4H, PPh3);
6.28 (s, 5H, C5H5); 5.24 (d, 1H, J=16.3, CH2); 5.08 (d,
25.0 (CH3). 31P {1H}-NMR (121 MHz, CD3COCD3) l:
17.6 (s) (major). H-NMR (400 MHz, CD3COCD3) l:
1
1
7.59–7.75 (m, 9H, PPh3); 7.43–7.57 (m, 6H, PPh3); 6.73
(dd, 1H, J=1.5, JPH=19.3, ꢀCH); 6.25 (s, 5H, C5H5);
1H, J=16.3, CH2); 4.98 (s, 1H, CH2OH
CH2OH); 3.94 (d, 1H, J=16.3, CH2); 3.70 (d, 1H,
J=16.3, CH2). 13C-NMR (100 MHz, CD3COCD3) l:
6 ); 4.61 (s, 1H,
5.25–5.35 (m, 1H, CH
6
OH); 5.00 (d, 1H, J=5.1,
6
CHOH
6
); 1.63 (d, 3H, J=6.6, CH3). 13C-NMR (100

S. Legoupy et al. / Journal of Organometallic Chemistry 567 (1998) 75–81
79
J
PH=6.6, ꢁCH2). 13C-NMR (100 MHz, CD3COCD3)
127.5–136.0 (Ph); 105.4 (CꢀC); 100.3 (C5H5); 90.8
(JCP=13.7, CꢀC); 62.3 (CH2OH); 61.5 (JCP=5.3,
CH2OH). 31P {1H}-NMR (121 MHz, CD3COCD3) l:
14.4 (s). IR (cm−1, neat): wNO 1710 (vs); wCꢀC 1868 (m).
HRMS: calc. for (C27H26NO3PRe)+: 630.1209; found:
630.1219.
l: 134.3 (JCP=9.9, o–Ph); 132.9 (JCP=2.7, p–Ph);
131.5 (JCP=58.7, i-Ph); 130.4 (JCP=11.1, m–Ph); 98.4
(C5H5); 66.9 (CH2OH); 51.6 (ꢁCH); 36.4 (JCP=5.7,
CH2ꢁ). 31P {1H}-NMR (121 MHz, CD3COCD3) l:
12.6 (s). IR (cm−1, neat): wNO 1731 (vs); 1614 (m).
HRMS: calc. for (C26H26NO2PRe)+: 602.1259; found:
602.1253.
4.1.6. [(p5-C5H5)Re(NO)(PPh3)(H2CꢁCHCH2CH2
OH)]+[BF4]− 6b
4.1.8. Preparation of h,i-unsaturated aldehyde and
ketone complexes
3-Buten-1-ol was used as alcohol. Yield: 83.0 mg,
0.118 mmol, 66%. Two diastereomers in a 84:16 ratio.
(major). 1H-NMR (400 MHz, CD2Cl2) l: 7.45–7.58
(m, 9H, PPh3); 7.22–7.34 (m, 6H, PPh3); 5.70 (s, 5H,
C5H5); 4.42–4.53 (m, 1H, ꢁCH); 3.68–3.78 (m, 1H,
CH2OH); 3.58–3.67 (m, 1H, CH2OH); 2.43–2.52 (m,
To complex 5c, 6a,b (50 mg) in DMSO (1.5 ml) IBX
(2.1 equivalents) was added by portions under nitrogen.
The mixture was stirred for 4 h at r.t. Water (2 ml) and
dichloromethane (10 ml) were added and the organic
phase was separated, washed twice with water, dried
over MgSO4. Solvents were removed by rotary evapora-
tion. The resulting yellow syrup was rapidly chro-
matographed on a short silica gel column (l:1.5 cm)
with use of 4:1 dichloromethane/acetone (v/v).
1H, ꢁCH2); 2.32–2.42 (m, 1H, CH2
1H, J=10.2, 4.1, JPH=6.6, ꢁCH2); 1.95–2.08 (m, 1H,
CH2
CH2OH). 13C-NMR (100 MHz, CD2Cl2) l: 133.3
6 CH2OH); 2.27 (ddd,
6
(JCP=9.9, o–Ph); 132.4 (JCP=2.7, p–Ph); 130.4
(JCP=59.5, i–Ph); 129.8 (JCP=11.1, m–Ph); 97.1
(C5H5); 64.2 (CH2OH); 48.6 (ꢁCH); 40.6 (C6 H2CH2OH);
4.1.9. [(p5-C5H5)Re(NO)(PPh3)(HCꢀCC(CH3)O)]+
[BF4]− 7b
38.5 (JCP=5.7, CH2ꢁ). 31P {1H}-NMR (121 MHz,
CD2Cl2) l: 10.7 (s) (minor). 1H-NMR partiel (400
MHz, CD2Cl2) l: 7.45–7.58 (m, 9H, PPh3); 7.22–7.34
(m, 6H, PPh3); 5.61 (s, 5H, C5H5); 3.68–3.78 (m, 1H,
CH2OH); 3.58–3.67 (m, 1H, CH2OH); 2.89–2.98 (m,
1H, ꢁCH); 2.63–2.71 (m, 1H, CH2CH2OH); 1.95–2.08
(m, 1H, ꢁCH2); 1.58–1.69 (m, 1H, CH2CH2OH). 13C
{1H}-NMR (100 MHz, CD2Cl2) l: 133.4 (JCP=9.2,
o–Ph); 132.5 (p–Ph); 129.8 (m–Ph); 97.8 (C5H5); 66.7
The reaction was performed starting from complex
1
5b. Yield: 37.9 mg, 0.054 mmol, 76%. H-NMR (400
MHz, CD3COCD3) l: 8.20 (d, 1H, JPH=18.4, CH);
7.58–7.77 (m, 9H, PPh3); 7.42–7.55 (m, 6H, PPh3); 6.28
(s, 5H, C5H5); 2.77 (s, 3H, CH3). 13C-NMR (100 MHz,
CD3COCD3) l: 192.3 (JCP=2.3, CO); 135.0 (JCP
10.7, o–Ph); 134.2 (JCP=2.7, p–Ph); 131.4 (JCP=11.4,
=
m–Ph); 109.9 (JCP=14.5, –CꢀC6 H); 101.3 (C6 ꢀCH);
(CH2OH); 50.6 (ꢁCH); 42.8 (C6 H2CH2OH); 39.0 (JCP=
101.1 (C5H5); 34.2 (CH3). 31P {1H}-NMR (121 MHz,
CD3COCD3) l: 17.1 (s). IR (cm−1, neat): wNO 1718
(vs); wCO 1680 (vs).
4.9, CH2=). 31P {1H}-NMR (121 MHz, CD2Cl2) l:
10.9 (s). IR (cm−1, neat): wNO 1718 (vs). HRMS: calc.
for (C27H28NO2PRe)+: 616.1416; found: 616.1409.
4.1.10. [(p5-C5H5)Re(NO)(PPh3)(H3CCꢀCCHO)]+
[BF4]− 7c
4.1.7. Preparation of [(p5-C5H5)Re(NO)(PPh3)(H2Cꢁ
CHCH2OH)]+[BF4]− 6a
Complex (p5-C5H5)Re(NO)(CH3)(PPh3) 1 (100 mg,
0.179 mmol) and CH2Cl2 (10 ml) were cooled to −
78°C and HBF4 ·OEt2 (85%, 32 ml, 0.18 mmol) was
added with stirring. After 30 min, a large excess of allyl
alcohol (2 ml) was added. The reaction mixture was
stirred for 1 h at −78°C, was then allowed to warm to
−23°C over the course of 1 h and was stirred overnight
at r.t. Solvent was removed by rotary evaporation. The
resulting residue was chromatographed on a silica gel
column with use of 4:1 dichloromethane/acetone (v/v)
to give compound 6a as a white–yellow oil. Yield: 97.4
mg, 0.141 mmol, 79%. Only one diastereomer was
The reaction was performed starting from complex
5c. Yield: 65.0 mg, 0.093 mmol, 65%. Two rotamers
42:58 (minor). 1H-NMR (400 MHz, CD3COCD3) l:
11.04 (s, 1H, CHO); 7.86–7.52 (m, 9H, PPh3); 7.24–
7.47 (m, 6H, PPh3); 6.30 (s, 5H, C5H5); 2.31 (s, 3H,
CH3). 13C-NMR (100 MHz, CD3COCD3) l: 183.9
(JCP=2.3, CHO); 135.9–129.8 (Ph); 119.4 (JCP=12.5,
CꢀC); 100.1 (C5H5); 93.1 (CꢀC); 14.5 (JCP=4.9, CH3).
31P {1H}-NMR (121 MHz, CD3COCD3) l: 17.6. IR
(cm−1, neat): wNO 1719 (vs); wCO 1667 (vs) (major).
1H-NMR (400 MHz, CD3COCD3) l: 10.05 (s, 1H,
CHO); 7.86–7.52 (m, 9H, PPh3); 7.24–7.47 (m, 6H,
PPh3); 6.29 (s, 5H, C5H5); 3.34 (s, 3H, CH3). 13C-NMR
(100 MHz, CD3COCD3) l: 185.5 (JCP=5.7, CHO);
135.9–129.8 (Ph); 126.8 (CꢀC); 101.5 (JCP=0.8, C5H5);
86.6 (JCP=13.8, CꢀC); 19.3 (JCP=1.9, CH3). 31P {1H}-
1
observed. H-NMR (400 MHz, CD3COCD3) l: 7.62–
7.71 (m, 9H, PPh3); 7.53–7.61 (m, 6H, PPh3); 6.10 (s,
5H, C5H5); 4.67–4.77 (m, 1H, ꢁCH); 4.28–4.37 (m, 1H,
CH2OH
4.09 (m, 1H, J=5.6, CH2
3.6, JPH=11.2, ꢁCH2); 2.24 (ddd, 1H, J=9.7, 3.6,
6
); 4.32–4.37 (m, 1H, J=5.6, CH2
6
OH); 4.00–
6
OH); 2.67 (ddd, 1H, J=11.2,
NMR (121 MHz, CD3COCD3) l: 17.6. IR (cm−1
neat): nNO 1719 (vs); nCO 1667 (vs).
,

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S. Legoupy et al. / Journal of Organometallic Chemistry 567 (1998) 75–81
4.1.11. [(p5-C5H5)Re(NO)(PPh3)(H2CꢁCHCHO)]+
[BF4]− 8a
The reaction was performed starting from complex
6a. Yield: 60.8 mg, 0.089 mmol, 61%. The spectroscopic
data are consistent with those previously reported by
Gladysz et al. [11].
J
J
PH=10.9, H2
6 CꢁCH–); 2.27 (m, 2H, J=4.3, 9.8,
PH=5.8, H2CꢁCH); 1.18 and 1.20 (2d, 6H, J=6.3,
6
CH3). 13C {1H}-NMR (CD3CN, 100 MHz) l: 139.7
(–C
(JCP=9.9, o–Ph), 132.9 (JCP=2.7, p–Ph); 131.3
(JCP=58.7, i–Ph); 131.1 and 131.0 (–CHꢁCH–CHOH
or –CHꢁCH–CHOH); 130.3 (JCP=11.1, m–Ph), 98.3
(C5H5), 67.4 (CHOH); 50.7 and 50.6 (H2CꢁCH), 36.3
and 36.2 (JCP=5.7, H2C
ꢁCH); 24.7 and 24.5 (CH3). 31
{1H}-NMR (CD2Cl2, 121 MHz) l: 11.0 (s). IR (cm−1
6 HꢁCH–CHOH or –CHꢁC6 H–CHOH); 134.0
6
6
4.1.12. Preparation of [(p5-C5H5)Re(NO)
6
(PPh3)(H2CꢁCH–CHꢁCH–C(CH3)O)]+[BF4]−
9
6
P
,
To complex 8a (520 mg, 0.76 mmol) and anhydrous
CH3CN (50 ml) methyl(triphenylphosphoranyli-
dene)ketone (506 mg, 1.59 mmol) was added. The
reaction mixture was stirred for 5 h at 65°C. The
solvent was removed by rotary evaporation. The result-
ing residue was added to a CH2Cl2/EtOH solution. The
resulting tan powder was collected by filtration, washed
with Et2O and dried under oil-pump vacuum to give
complex 9 as a white-yellow solid. Yield: 402 mg, 0.55
mmol, 73%. Only one diastereomer was observed.
1H-NMR (CD3CN, 400 MHz) l: 7.55–7.68 (m,
9H, PPh3); 7.39–7.48 (m, 6H, PPh3); 6.47 (dd, 1H,
neat): wNO 1720 (vs). HRMS calc. for C29H30NO2PRe:
642.1573, found: 642.1571.
4.1.14. Preparation of [(p5-C5H5)Re(NO)(PPh3)(H2Cꢁ
CHCH2OCOCH3)]+[BF4]− 11
Pyridine (2 ml, 25 mmol) and acetic anhydride (1 ml,
11 mmol) were added to complex 6a (200 mg, 0.29
mmole) with stirring. After 24 h of stirring at r.t.,
CH2Cl2 (10 ml) was added to the reaction mixture. The
solution was washed with aqueous KH2PO4, brine and
water. The organic phase was dried on MgSO4 and the
volatile part was removed in vacuo. To the resulting
residue was added a 1:1 dichloromethane/diethyl ether
solution. The resulting tan powder was collected by
filtration, washed with diethyl ether and dried under
oil-pump vacuum to give complex 11 as a brown solid.
Yield: 148 mg, 0.203 mmol, 70%. Only one
diastereomer was observed. 1H-NMR (400 MHz,
CD3NO2) l: 7.60–7.72 (m, 9H, PPh3); 7.52–7.58 (m,
6H, PPh3); 5.98 (s, 5H, C5H5); 4.43–4.60 (m, 3H, CH2O
and ꢁCH); 2.69 (ddd, 1H, J=10.7, 4.6, JPH=10.7,
H2Cꢁ); 2.36 (ddd, 1H, J=9.7, 4.6, JPH=6.6, H2Cꢁ);
2.06 (s, 3H, CH3). 13C-NMR (100 MHz, CD3NO2) l:
172.3 (CO); 134.8 (JCP=9.9, o–Ph); 133.7 (JCP=2.7,
p–Ph); 131.5 (JCP=59.9, i–Ph); 130.9 (JCP=11.1, m–
J=9.7, 15.8, H
HC=CH–CO); 5.83 (s, 5H, C5H5); 4.94 (m, 1H, J=
9.2, 9.7, 10.7, PH=2.0, H2CꢁCH–); 2.73 (ddd,
1H, J=9.2, 4.6, JPH=10.7, H2
6 C=CH–CO); 6.29 (d, 1H, J=15.8,
6
J
6
6
CꢁCH–); 2.48 (ddd, 1H,
J=10.7, 4.6,
JPH=6.1, H6 2CꢁCH); 2.18 (s, 3H,
CH3). 13C {1H}-NMR (CD3CN, 100 MHz) l: 197.9
(CO); 149.2 (CHꢁCH); 134.1 (JCP=9.9, o–Ph), 133.1
(JCP=3.0, p–Ph); 130.9 (CHꢁCH); 130.4 (JCP
11.6, m–Ph), 99.1 (C5H5), 45.6 (H2CꢁCH), 38.7 (JCP
=
=
6
6.1, H2C
6
ꢁCH); 27.1 (CH3). 31P {1H}-NMR (CD3CN,
121 MHz) l: 11.1. IR (cm−1, neat): wNO 1726 (vs).
HRMS calc. for C29H28NO2PRe: 640.1417, found:
640.1415.
Ph); 99.2 (C5H5); 69.7 (CH2O); 44.4 (ꢁCH); 37.6 (JCP
=
6.1, ꢁCH2); 21.0 (CH3). 31P {1H}-NMR (121 MHz,
CDCl3) l: 10.3. HRMS: calc. for (C28H28NO3PRe)+:
644.1366; found: 644.1376.
4.1.13. Preparation of [(p5-C5H5)Re(NO)
(PPh3)(H2CꢁCH–CHꢁCH–CH(CH3)OH)]+[BF4]− 10
Complex 9 (110 mg, 0.15 mmol) and anhydrous
methanol (17 ml) were cooled to −20°C and NaBH4
(8.5 mg, 0.225 mmol) was added with stirring. The
reaction mixture was stirred for 20 min at this tempera-
ture then hydrolysed. The organic compounds were
extracted three times with CH2Cl2. The organic phases
were dried and solvents were removed in vacuo. The
resulting residue was chromatographed on a silica gel
column with use of 1:1 dichloromethane/diethyl ether/
hexane solution. Complex 10 was isolated as a grey
solid. Two diastereomers in a 55:45 ratio. Yield: 75.0
4.1.15. Preparation of (p5-C5H5)Re(NO)(PPh3)(CH2
CH(CH2OC(O)CH3))–(CH(CO2CH3)2) 12
In a flask sodium hydride (3 mg, 0.125 mmol), THF
(4 ml) and dimethylmalonate (18 ml, 0.157 mmol) were
added. After 15 min of stirring, a solution of the com-
plex
[(p5-C5H5)Re(NO)(PPh3)(H2CꢁCHCH2OAc)]+
BF4− 11 (100 mg, 0.137 mmol) in THF (2 ml) was
added and the reaction mixture was stirred for 4 h.
Dichloromethane (20 ml) was then added, the solution
was washed with a 10% aqueous KOH, brine and
water. The organic phase was dried on MgSO4 and the
solvents were removed in vacuum. The resulting residue
was chromatographed on a 3 cm silica gel column with
use of 4:1 dichloromethane/acetone (v/v). The complex
12 was isolated as a yellow oil. Yield: 81.5 mg, 0.095
1
mg, 0.103 mmol, 68%. H-NMR (CD3CN, 400 MHz)
l: 7.32–7.66 (m, 15H, PPh3); 5.93 and 5.89 (2dd, 2H,
J=5.7, 12.8, CH
C5H5); 5.53 and 5.49 (2dd, 2H, J=9.6, 12.8, H
CHOH); 5.09 and 5.06 (2m, 2H, H2CꢁCH–); 4.36 and
4.32 (2m, 2H, CH–OH); 2.68 (dt, 2H, J=4.3, 10.9,
6
CHOH); 5.75 and 5.74 (2s, 10H,
6
CꢁCH–
6
1
6
mmol, 69%. H-NMR (400 MHz, CDCl3) l: 7.31–7.43

S. Legoupy et al. / Journal of Organometallic Chemistry 567 (1998) 75–81
81
[3] (a) A. Cutler, D. Ehntholt, P. Lennon et al., J. Am. Chem. Soc.
97 (1975) 3149. (b) P.F. Boyle, K.M. Nicholas, J. Org. Chem. 40
(1975) 2682. (c) K.M. Nicholas, J. Am. Chem. Soc. 97 (1975)
3254. (d) M. Marsi, M. Rosenblum, J. Am. Chem. Soc. 106
(1984) 7264.
[4] (a) J. Gonzalez, M. Sabat, W.D. Harman, J. Am. Chem. Soc.
115 (1993) 8857. (b) H. Chen, L.M. Hodges, R. Liu, W.C.
Stevens Jr., M. Sabat, W.D. Harman, J. Am. Chem. Soc. 116
(1994) 5499. (c) M.E. Kopach, W.D. Harman, J. Am. Chem.
Soc. 116 (1994) 6581. (d) L.M. Hodges, M.W. Moody, W.D.
Harman, J. Am. Chem. Soc. 116 (1994) 7931. (e) R. Liu, H.
Chen, W.D. Harman, Organometallics 14 (1995) 2861. (f) M.L.
Spera, W.D. Harman, J. Am. Chem. Soc. 119 (1997) 8843.
[5] D. Schinzer, H. Ba¨rmann, Angew. Chem. Int. Ed. Engl. 35
(1996) 1678.
(m, 15H, PPh3); 5.02 (s, 5H, C5H5); 4.61 (dd, 1H,
J=11.2, 3.6, CH2OAc); 3.98 (dd, 1H, J=11.2, 7.6,
CH2OAc); 3.69 (s, 3H, CO2CH3); 3.52 (s, 3H,
CO2CH3); 3.43 (d, 1H, J=7.1, CH
2.63 (m, 1H, CHCH2Re); 2.02 (s, 3H, C(O)CH3); 1.62–
1.79 (m, 2H, CH2Re). 13C-NMR 100 MHz, CD3NO2)
l: 171.7 (CO); 170.4 (CO); 170.3 (CO); 136.8 (JCP
6 (CO2CH3)2); 2.53–
6
=
51.5, i–Ph); 134.2 (JCP=10.3, o–Ph); 130.6 (JCP=2.3,
p–Ph); 129.0 (JCP=9.9, m–Ph); 90.6 (JCP=1.5, C5H5);
68.1 (CH2O); 58.1 (C
52.6 (CO2CH3); 49.4 (JCP=4.2, C
(OC(O)CH3); 0.5 (JCP=5.3, C
6
H(CO2CH3)2); 52.8 (CO2C
HCH2Re); 21.8
H2Re). 31P {1H}-NMR
6 H3);
6
6
6
6
(121 MHz, CDCl3) l: 24.1. IR (cm−1, neat): wNO 1732
(vs); wCO 1629 (vs). HRMS: calc. for (C33H35NO7PRe)+:
775.1710; found: 775.1732.
[6] F. Agbossou, E.J. O’Connor, C.M. Garner, et al., Inorg. Synth.
29 (1992) 211.
[7] See for example: (a) J.J. Kowalczyk, A.M. Arif, J.A. Gladysz,
Chem. Ber. 124 (1991) 729; Organometallics 10 (1991) 1079. (b)
J. Pu, T.-S. Peng, C.L. Mayne, A.M. Arif, J.A. Gladysz,
Organometallics 12 (1993) 2686. (c) T.-S. Peng, Y. Wang, A.M.
Arif, J.A. Gladysz, Organometallics 12 (1993) 4535. (d) T.-S.
Peng, C.H. Winter, J.A. Gladysz, Inorg. Chem. 33 (1994) 2534.
(e) T.-S. Peng, J. Pu, J.A. Gladysz, Organometallics 13 (1994)
929.
Acknowledgements
We thank Dr P. Guenot for performing the mass
spectral experiments.
[8] S. Legoupy, C. Cre´visy, J.-C. Guillemin, R. Gre´e, Tetrahedron
Lett. 37 (1996) 1225.
[9] (a) J.J. Kowalczyk, S.K. Agbossou, J.A. Gladysz, J. Organomet.
Chem. 397 (1990) 333. (b) J.M. Fernandez, J.A. Gladysz,
Organometallics 8 (1989) 207. (c) J.A. Gladysz, B.J. Boone,
Angew. Chem. Int. Ed. Engl. 36 (1997) 551.
[10] (a) M. Frigerio, M. Santagostino, M. Tetrahedron Lett. 35
(1994) 8019. (b) M. Frigerio, M. Santagostino, S. Sputore, G.
Palmisano, J. Org. Chem. 60 (1995) 7272.
References
[1] J.P. Collman, L.S. Hegedus, R.O. Finke, J.R. Norton, Principles
and Applications of Organotransition Metal Chemistry, 2nd,
University Science Books, Mill Valley, CA, 1987.
[2] (a) S. Padmanabhan, K.M. Nicholas, Tetrahedron Lett. 24
(1983) 2239. (b) M. Saha, K.M. Nicholas, J. Org. Chem. 49
(1984) 417. (c) W.A. Smit, A.A. Schegolev, A.S. Gybin, G.S.
Mikaelian, Synthesis (1984) 887. (d) K.M. Nicholas, Acc. Chem.
Res. 20 (1987) 207. (e) J. Ju, B.R. Reddy, M. Khan, K.M.
Nicholas, J. Org. Chem. 54 (1989) 5426. (f) C. Mukai, K. Suzuki,
K. Nagami, M. Hanaoka, J. Chem. Soc. Perkin Trans I (1992)
141.
[11] Y. Wang, F. Agbossou, D.M. Dalton, Y. Liu, A.M. Arif, J.A.
Gladysz, Organometallics 12 (1993) 2699.
[12] S. Legoupy, C. Cre´visy, J.-C. Guillemin, R. Gre´e, Organometal-
lics 16 (1997) 1822.
[13] (a) T.-S. Peng, A.M. Arif, J.A. Gladysz, J. Chem. Soc. Dalton
Trans. (1995) 1857. (b) T.-S. Peng, J.A. Gladysz, Tetrahedron
Lett. 31 (1990) 4417. (c) C.M. Garner, J.M. Fernandez, J.A.
Gladysz, Tetrahedron Lett. 30 (1989) 3931.
.
.