Organosamariums: Preparation using diiodosamarium and reactivity in tetrahydropyran

Article abstract of DOI:10.1016/S0022-328X(98)00666-4

Diiodosamarium prepared in tetrahydropyran reduces allylic, benzylic and alkyl halides at 0 or -15°C to give organosamariums which are stable under these conditions. The reactivity of these organometallics has been explored, showing that they are very sel

Full text of DOI:10.1016/S0022-328X(98)00666-4

Journal of Organometallic Chemistry 567 (1998) 39–47
Organosamariums: preparation using diiodosamarium and reactivity in
tetrahydropyran
Be´atrice Hamann-Gaudinet, Jean-Louis Namy *, Henri B. Kagan
Laboratoire de Synthe`se Asyme´trique, Associe´ au CNRS, Institut de Chimie Mole´culaire d’Orsay, Uni6ersite´ Paris-Sud, 91405 Orsay, France
Received 10 October 1997; received in revised form 3 December 1997
Abstract
Diiodosamarium prepared in tetrahydropyran reduces allylic, benzylic and alkyl halides at 0 or −15°C to give organosamar-
iums which are stable under these conditions. The reactivity of these organometallics has been explored, showing that they are
very selective reagents. © 1998 Elsevier Science S.A. All rights reserved.
Keywords: Diiodosamarium; Tetrahydropyran; Organosamariums; Allylic halides; Benzylic halides; Alkyl halides
1. Introduction
tion of h-ketols by addition to aldehydes). Ito has also
reported that the use of THP as solvent for SmI2 allows
the generation of (h-aminoalkyl)samarium(III) [8]. We
wish to report here that stable organosamariums are
easily prepared according to Eq. 1 with SmI2 in tetrahy-
dropyran (THP) instead of THF.
Organosamariums may be generated in THF from
organic iodides and bromides and SmI2 according to
Eq. 1. However, they are quite unstable and need to be
trapped as soon as possible by electrophiles [1,2].
2. Results and discussion
Alkyl samariums abstract hydrogen from THF to
give alkanes unless they are kept at −78°C [3]. Wurtz
coupling reactions are exclusively observed in reactions
of allylic or benzylic halides with SmI2 in THF [4].
On the other hand, stable organosamariums can be
prepared in THF by using SmCp2 [2] [5] or Sm(OTf)2/
LiOTf [6] as the reducing agent. We have previously
described the beneficial effect of THP in the reaction of
SmI2 (prepared in THP) on acid chlorides RCOCl for
the formation of isolable acylsamarium species
RC(O)SmI2 [7]. The competitive coupling to give sa-
marium-enediolates could be avoided, allowing the use
of acylsamariums as nucleophilic reagents (e.g. forma-
We found that isolable allylsamarium species are
formed in THP at −15°C by the action of SmI2 on
(E)-1-iodo-2-dodecene (Table 1 Scheme 1). The pres-
ence of organometallic species was established by
quenching with D2O and product analysis. Deuteration
has been clearly demonstrated with iodide 1 giving a
mixture of olefins 2 and 3, with a high content of
deuteration (85%) for 3. Quenching after 15 min by an
electrophile such as butanone gave regioselectively, and
in good yield, the alcohol resulting from attack by the
terminal position of the allylsamarium.
Obviously, the regioselectivity of electrophilic attack
on the allylic samarium species strongly depends upon
the electrophiles: D2O reacts predominantly on the
more substituted carbon, whereas butanone almost ex-
clusively attacks the less hindered carbon. Furthermore,
* Corresponding author. Tel.: +33 69 154743; fax: +33 69
154680; e-mail: jelonamy@icmo.u-psud.fr
0022-328X/98/$19.00 © 1998 Elsevier Science S.A. All rights reserved.
PII S0022-328X(98)00666-4

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B. Hamann-Gaudinet et al. / Journal of Organometallic Chemistry 567 (1998) 39–47
Table 1
Deuteration of allylic samarium species
Scheme 2. Regioselectivity of reactions of allylic samarium species.
SmI2. Quenching by an electrophile such as 2-octanone
gave regioselectively, and in good yield, the alcohols
resulting from attack by the terminal position of the
allylsamarium compounds; propargylsamarium dihalide
gives mainly allenic alcohol (Table 4)
a Dropwise addition of 1 in 10 min, then standing time t (min)
before deuterolysis.
b The conversion of 1 into alkenes is quantitative, the ratio 2/3 is
determined by GC and percentages of deuteration by GC/MS.
The above procedure also applies to the preparation
of benzylic samarium diiodide as evidenced by some
reactions with benzylic bromides (deuterolysis or addi-
tion on 2-octanone). In the case of 4-t-Bu benzyl bro-
mide, deuterolysis leads to quantitative conversion into
hydrocarbons; the ratio (82:18) is measured by GC,
(Scheme 3).
The generation of stable alkyl samarium complexes
from SmI2 is a difficult task which can be carried out by
the use of THP as solvent, as evidenced by the follow-
ing experimental results (deuterolysis or addition to
2-butanone) (Scheme 4). In contrast to allylic and
benzylic halides, reduction of alkyl halides to
organometallic species must be performed in the pres-
ence of HMPA as a co-solvent. The conversions of the
1-iodo and 2-iodododecanes are almost quantitative
(\95%); after deuterolysis the dodecanes are formed
with a high rate of deuterium incorporation (85%). The
alkyl samarium diiodide reacts slowly with ketones, in
order to enhance the rates of the reactions (and prevent
any organometallic degradation) TMSCl is added as
previously reported [3].
the degradation of the organometallic species (pre-
sumably through a reaction with THP) preferentially
occurs by reaction on the terminal position of the
allylic species. Assuming that a p3-allyl samarium spe-
cies is formed [5] these results are illustrated in Scheme
2. A thorough interpretation of the reactivity of this
organometallic requires further investigation.
The organosamarium prepared from allyl iodide is
much more stable than the one described above. It is
prepared at 0°C and can be used for at least 24 h
provided it is stored at 0°C. The allyl transfer has been
realized on various functions such as aldehydes, ke-
tones, imines, esters h-,i- or k-keto esters. The low
basicity of the allylsamarium reagent is highlighted by
its successful addition to allyl acetoacetate, a ketone
prone to enolization [9,10]. The allylation is very
stereoselective both on camphor and fenchone (Table
2).
The Grignard technique (method A) is clearly supe-
rior to the Barbier technique (method B) and avoids
by-products due to ketone pinacolization or acid chlo-
ride decarbonylation (see Table 3).
Organosamariums have been successfully prepared in
a similar way from other allylic halides (and propargyl
bromide). Cinnamyl halides and 3-bromocyclohexene,
however give Wurtz coupling products on reaction with
Reduction of cis and trans 1-iodo-4-tert-butylcyclo-
hexane into organometallic species followed by trap-
ping of the resulting products with butanone leads in
both experiments to the same diastereomeric mixture of
alcohols (the trans isomer broadly predominates)
(Scheme 5).
Scheme 1. Preparation and reactions of allylic samarium species.

B. Hamann-Gaudinet et al. / Journal of Organometallic Chemistry 567 (1998) 39–47
41
Table 2
Reaction of allylsamarium diiodide in THP on various functional groups
a Reactions on 2 mmol of substrate: 2 eq. SmI2 and 1 eq. allyl iodide in THP (1 h, 0°C), then addition of substrate (0°C to rt), acidic hydrolysis,
isolated yield by respect to substrate.
b Reaction at 0°C.
These results are consistent with the transient forma-
tion of an alkyl radical, which undergoes further reduc-
tion into an organometallics species (Scheme 6).
4. Experimental
4.1. General
1H and 13C-NMR spectra were recorded at 250 and
63 MHz, respectively on a Bruker AM 250 instrument
(unless otherwise stated). Chemical shifts are reported
in ppm (l) downfield from TMS. Coupling constants
are reported in Hertz. Infrared (IR) spectra were
recorded neat on a FT-IR IFS 66 Bruker and are
3. Conclusions
Organosamariums are easily prepared in tetrahy-
dropyran by SmI2 reduction of allylic, benzylic or alkyl
halides. The organometallics which are obtained in this
solvent are much more stable than in THF. However,
these compounds can react with many functionalities.
The selectivity of these reagents can be highlighted by
their successful addition to the keto group of keto
esters or keto amides.
reported in cm−1
.
Mass spectra (MS) data were determined on a GC/
MS Ribermag R10-10 instrument. Chemical ionisation
(CI) was carried out using NH3 as the reactant gas and
electronic impact was performed at 70 eV. High resolu-

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B. Hamann-Gaudinet et al. / Journal of Organometallic Chemistry 567 (1998) 39–47
Table 3
Reactions of allylsamarium diiodide (prepared at 0°C in THP from 2 equivalents of SmI2) on acetophenone and phenylacetyl chloride
a Method A: organosamarium prepared at 0°C in 1 h followed by addition of electrophile; reaction time 1 h. Method B: allyl iodide and
electrophile are mixed and added to SmI2 in THP at 0°C; reaction time 2 h.
b GC yield.
c Reaction time 15 h; full transformation after 2 h (method A) in the presence of 1% NiCl2 dppe.
tion mass spectra were determined on a GC/MS
Finningan-MAT-95-S. Flash chromatography was per-
formed on silica gel (Merck 230–240 mesh; 0.0040–
0.0630 mm).
procedure was used for other allylic and benzylic
halides except the preparation was performed at
−15°C and the halide was added dropwise to SmI2.
All commercially available organic compounds were
distilled before use, (E)-1-iodo-2-dodecene, cis and
trans 1-iodo-4-tert-butylcyclohexane and 2-iododode-
cane were prepared according to literature procedures
[11–13]. Samarium powder (40 mesh) was purchased
from Labelcomat Company. Tetrahydropyran was dis-
tilled under argon from sodium benzophenone ketyl,
HMPA was distilled from CaH2 and degassed immedi-
ately prior to use. All the reactions were carried out
under argon in Schlenk tubes using standard vacuum
line techniques.
4.4. Preparation of alkylsamarium diiodide
A total of 2.1 ml of HMPA (12 mmol) was added to
a slurry of SmI2 (4 mmol) in 15 ml of THP under argon
at 20°C. The mixture turned violet, the alkyl iodide was
then added (2 mmol in 2 ml of THP). The mixture was
kept at 20°C for 2 min, it was then cooled to −20°C.
4.5. Procedure for reactions with allylsamarium
diiodide
In a Schlenk tube under argon, allylsamarium diio-
dide (2 mmol) in 6 ml of THP (Section 4.3) and 1 mmol
of substrate in 2 ml of THP were mixed and stirred at
0°C. The mixture turned yellow within a reaction time
of 0.5 h. It was then quenched with HCl (0.1 M) to
obtain a clear solution and extracted with ether. The
combined extracts are washed with sodium thiosulfate
and brine. The organic layer is dried over MgSO4. After
removal of solvent the crude material is purified by
flash chromatography on silica gel. The same procedure
is used for other allylic and benzylic samarium dihalides
except that the reactions are performed from −15 to
20°C during 3 h.
4.2. Preparation of SmI2 in tetrahydropyran
To a mixture of samarium powder (601 mg, 4.00
mmol) and 1,2-diiodoethane (1.127 g, 4.00 mmol) under
argon at room temperature THP was added (4.00 ml)
with vigorous stirring. After a short induction period a
slightly exothermic reaction took place and the mixture
turned dark blue. After 8 h at room temperature, a
slurry of SmI2 was obtained.
4.3. Preparation of allylsamarium diiodide
To a slurry of SmI2 (4 mmol) in 4 ml of THP under
argon at 0°C, allyl iodide (0.336 g, 2 mmol) in THP (2
ml) was added with stirring. The mixture was kept at
0°C for 1 h and turned light blue (turquoise). The allyl
samarium diiodide was obtained as a slurry. The same
4.6. Procedure for reactions with alkylsamarium
diiodides
In a Schlenk tube under argon, alkylsamarium diio-

B. Hamann-Gaudinet et al. / Journal of Organometallic Chemistry 567 (1998) 39–47
43
Table 4
Reactions of allylic samariums species prepared from allylic halides, with 2-octanone
a Reactions on 2 mmol of organic halide, 2 eq. SmI2 in THP (4 mL of solvent, 15 min, −15°C), then addition of 0.66 eq. ketone (−15°C to
rt, 3 h), acidic hydrolysis, isolated yield by respect to ketone.
dide (2 mmol) in 15 ml of THP and 2 ml of HMPA
(Section 4.4) were mixed with 1 mmol of substrate in
2 ml of THP and 0.4 ml (3.18 mmol) of chloro-
trimethylsilane and stirred at −20°C. The tempera-
ture rose to 20°C within 4 h, the mixture turned
yellow during this reaction time. Quenching and isola-
tion of products was performed as described above
(Section 4.5)
4.7.3. Undecen-4-ol
Yield 75%, as colorless oil; IR wmax (neat)/cm−1
:
1
3357, 2926, 2856, 1641, 1467, 1378, 995, 912; H-NMR
(250 MHz, CDCl3) l: 5.98–5.71 (1H, ddt, J=16.6,
10.7, 7.3 Hz), 5.23–5.03 (2H, m), 3.72–3.51 (1H, m),
2.39–2.11 (2H, m), 1.89–1.13 (12H, m), 0.87 (3H, t,
J=6.3 Hz); 13C-NMR (62.9 MHz, CDCl3) l: 135.00,
118.03, 70.75, 42.00, 36.88, 31.88, 29.68, 29.34, 25.73,
22.71, 22.69, 14.14; MS m/z 129 (M+ –C3H5), 69
(100.00), 55; CI/NH3 m/z 170 (MH+), 188 (MNH4+).
HRMS Calc. for C11H22O (M–C3H5)+ 152.1565
Found 152.1553.
4.7. Identification of products
4.7.1. 3-Deutero-1-dodecen
MS m/z 169 (M+), 141 (M+ –C2H4), 126 (M+
–
C2H4–CH3), 112, 98, 84, 70, 56 (100.00), 43. (1-do-
decene: 168, 140, 125, 111, 97, 83, 69, 55, 41 (100.00).
4.7.4. (1R,2R) Endo-1-(prop-2%-enyl)-1,7,7-trimethyl-
bicyclo[2.2.1]heptan-2-ol
Yield 75%, as orange oil; IR wmax (neat)/cm−1: 3568
(OH), 3074, 2949, 1636, 1457, 1389, 1272, 1120, 911;
1H-NMR (200 MHz, CDCl3) l: 6.03–5.80 (1H, ddt,
J=16.6, 9.8, 7.8 Hz), 5.18–5.06 (2H, m), 2.27 (2H, dd,
J=7.8, 1.0 Hz), 2.12–1.87 (1H, dt, J=3.6, 12.8 Hz),
1.85–1.56 (3H, m), 1.53–1.28 (3H, m), 1.07 (3H, m),
4.7.2. (2E) 1-deutero-2-dodecen
MS m/z 169 (M+), 141 (M+ –C2H4), 126 (M+
–
C2H4-CH3), 112, 98, 84, 70, 56 (100.00), 43. ((2E)
2-dodecene: 168, 140, 125, 111, 97, 83, 69, 55
(100.00), 41).

44
B. Hamann-Gaudinet et al. / Journal of Organometallic Chemistry 567 (1998) 39–47
Scheme 3. Preparation and reactions of benzylic samarium species.
0.83 (6H, m); 13C-NMR (50.8 MHz, CDCl3) l: 134.99,
118.91, 79.71, 52.18, 49.40, 45.98, 45.04, 44.56, 30.55,
27.05, 21.43, 20.99, 10.97; MS m/z 194 (M+), 153
(M+ –C3H5), 109, 95 (100.00), 69, 41; CI/NH3 m/z 195
(MH+), 212 (MNH4+). HRMS Calc. for C13H22O
194.1671 Found 194.1657.
4.7.6. N-Cyclopropyl-1-allylbenzylamine
Yield 62%, as colorless oil; 1H-NMR (250 MHz,
CDCl3) l: 7.40–7.08 (5H, m), 5.75–5.53 (1H, ddt,
J=16.6, 10.7, 7.3 Hz), 5.15–4.82 (2H, m), 3.71 (1H, t,
J=7.5 Hz), 2.53–2.28 (2H, m), 2.00 (1H, s), 1.91 (1H,
q, J=5 Hz), 0.39–0.13 (4H, m); 13C-NMR (62.9 MHz,
CDCl3) l: 144.17, 135.52, 128.30, 127.36, 126.97,
117.29, 63.02, 42.13, 29.13, 6.82, 6.10; MS m/z 187
(M+), 146 (M+ –C3H5), 131 (M+ –C3H6N), 91
(100.00), 77 41;CI/NH3 m/z 188 (MH+), 205 (MNH4+
). HRMS Calc. for C13H17N 187.1361 Found 187.1344.
4.7.5. (1R,2R)
1-(prop-2%-enyl)-1,3,3-Trimethyl-2-norbornanol
Yield 67%, as orange oil; IR wmax (neat)/cm−1: 3499
(OH), 3075, 2948, 1637, 1456, 1390, 1239, 1065, 977;
1H-NMR (250 MHz, CDCl3) l: 6.09–5.90 (1H, m),
5.17–5.07 (2H, m), 2.39 (1H, dd, J=14.0, 6.0 Hz), 2.19
(1H, dd, J=14.0, 8.0 Hz), 1.03 (3H, s), 1.00 (3H, s),
0.89 (3H, s); 13C-NMR (62.9 MHz, CDCl3) l: 135.86,
119.47, 79.42, 52.28, 50.04, 44.37, 41.01, 40.71, 30.62,
27.75, 25.04, 22.65, 18.11; MS m/z 194 (M+), 153
(M+ –C3H5), 109, 95 (100.00), 69, 41; CI/NH3 m/z 195
(MH+), 212 (MNH4+). HRMS Calc. for C13H22O
194.1671 Found 194.1663.
4.7.7. 4-Phenylheptadi-1,6-en-4-ol
Yield 88%, as orange oil; IR wmax (neat)/cm−1: 3466
1
(OH), 2932, 1641, 1446, 1259, 1030, 915, 701; H-NMR
(250 MHz, CDCl3) l: 7.36–7.11 (5H, m), 5.51 (2H,
ddt, J=14.6, 10.2, 7.5 Hz), 5.02 (4H, m), 2.67–2,38
(4H, syste`me AB); 13C-NMR (62.9 MHz, CDCl3) l:
145.78, 133.45, 128.11, 125.34, 119.14, 75.09, 46.83; SM
m/z 170 (M+ –OH), 147 (M+ –C3H5), 105 (100.00), 77
(M+ –C7H11O); CI/NH3 m/z 189 (MH+), 206 (MNH4+
). HRMS Calc. for C13H16O (M–C3H5)+ 147.0810;
Found 147.0796.
Scheme 5. Preparation and reactions of cycloalkylsamarium diio-
dides.
Scheme 4. Preparation and reactions of alkyl samarium species.

B. Hamann-Gaudinet et al. / Journal of Organometallic Chemistry 567 (1998) 39–47
45
Scheme 6. Mechanistic scheme for the formation of cycloalkylsamarium species.
4.7.8. 7-Bromo-4-(prop-2’-enyl)hept-1-en-4-ol
5.75–5.50 (1H, ddt, J=16.6, 10.7, 7.3 Hz), 5.03–4.91
(2H, m), 2.67–2.54 (2H, m), 2.48–2.16 (3H, m), 2.12–
1.97 (1H, m), 1.95–1.38 (2H, m); 13C-NMR (50.8 MHz,
CDCl3) l: 171.57, 142.92, 131.96, 128.61, 127.45,
125.03, 119.31, 86.93, 48.20, 31.48, 29.15, 16.16; MS
Yield 72%, as yellow oil; IR wmax (neat)/cm−1: 3435
1
(OH), 3076, 2930, 1640, 1445, 1253, 997, 917; H-NMR
(200 MHz, CDCl3) l: 5.91–5.62 (2H, ddt, J=16.6,
10.7, 7.3 Hz), 5.13–5.00 (4H, m), 3.35 (2H, t, J=6.6
Hz), 2.16 (4H, dd, J=8.2, 0.8 Hz), 1.98–1.38 (4H, m);
13C-NMR (50.8 MHz, CDCl3) l: 133.28, 119.05, 73.05,
m/z 175 (M+ –C3H5), 147, 105 (100.00), 77 (M+
–
C8H11O2), 55; IC/NH3 m/z 217 (MH+), 234 (MNH4+).
Anal Calc. for C14H16O2 (216.27): C: 77.75, H: 7.46;
Found: C: 77.72, H: 7.29. HRMS Calc. for C14H16O2
(M–C3H5)+ 175.0759 Found 175.0748.
43.66, 37.58, 34.35, 26.93; MS m/z 191–193 (M+
–
–
C3H5), 149–151, 121–123 (M+ –C7H11O), 111 (M+
C4H6Br), 69, 41 (100.00); IC/NH3 m/z 233–235
(MH+), 250–252 (MNH4+). HRMS Calc. for
C18H19BrO (M–C3H6Br)+ 111.0810; Found 111.0796.
4.7.12. 1-(prop-2’-enyl)-1-Phenylbutanolide
Yield 70%, as yellow oil; IR wmax (neat)/cm−1: 2936,
1779 (lactone), 1641, 1448, 1272, 1193, 925, 764, 703;
1H-NMR (250 MHz, CDCl3) l: 7.59–7.13 (5H, m),
5.82–5.45 (1H, m), 5.35–5.4.94, (2H, m), 2.94–2.28
(6H, m); 13C-NMR (62.9 MHz, CDCl3) l: 176.44,
143.00, 131.58, 128.46, 127.64, 124.60, 119.89, 88.50,
46.64, 33.34, 28.70; MS m/z 161 (M+ –C3H5), 133, 115,
105 (100.00), 91, 77 (M+ –C7H10O), 51; CI/NH3 m/z
203 (MH+), 220 (MNH4+). HRMS Calc. for C10H9O2
(M–C3H5)+ 161.0603; Found 161.0600.
4.7.9. N-Benzyl-2-hydroxy-2-phenylpent-4-enamide
Yield 75%, as viscous colorless oil; IR wmax (neat)/
cm−1: 3400 (OH), 2927, 1659 (CONHCH2Ph), 1523,
1
1361 (CONHCH2Ph), 1260, 1142, 1075, 921, 728; H-
NMR (250 MHz, CDCl3) l: 7.60–7.46 (2H, m), 7.38–
6.90 (8H, m), 5.73–5.50 (1H, ddt, J=16.6, 10.7, 7.3
Hz), 5.20–5.06 (2H, m), 4.42–4.13 (2H, syste`me AB),
3.16 (1H, s), 3.14–2.61 (2H, AB system); 13C-NMR
(62.9 MHz, CDCl3) l: 173.28, 141.84, 138.02, 132.66,
128.57, 128.26, 127.65, 127.48, 127.36, 125.33, 120.87,
77.69, 44.38, 43.26; MS m/z 281 (M+), 240 (M+
–
4.7.13. 4-Benzylheptadi-1,6-en-4-ol
C3H5), 147(M+ –C10H11O) 105, 91 (M+ –C11H12NO2),
77, 41; CI/NH3 m/z 282 (MH+), 299 (MNH4+). HRMS
Calc. for C18H19NO2 281.1416; Found 281.1416.
Yield 60%, as yellow oil; IR wmax (neat)/cm−1: 3456
1
(OH), 2927, 1640, 1453, 1261, 915, 703; H-NMR (250
MHz, CDCl3) l: 7.29–7.03 (5H, m), 5.95–4.96 (2H,
ddt, J=16.6, 10.7, 7.3 Hz), 5.15–4.96 (4H, m), 2.69
(2H, s), 2.13 (4H, d, J=7.3 Hz), 1.58 (OH); 13C-NMR
(62.9 MHz, CDCl3) l: 137.17, 133.78, 130.78, 128.23,
4.7.10. Methyl-2-hydroxy-2-phenylpent-4-enoate
Yield 68%, as yellow oil; IR wmax (neat)/cm−1: 3509
(OH), 2856, 1741, 1643, 1494, 1350, 1232, 925, 865,
126.54, 118.86, 73.52, 45.40, 43.48; MS m/z 161 (M+
–
1
699; H-NMR (200 MHz, CDCl3) l: 7.58–7.11 (5H,
C3H5), 111 (M+ –C7H7), 91 (100.00, M+ –C7H11O), 69,
41; IC/NH3 m/z 203 (MH+), 220 (MNH4+). HRMS
Calc. for C11H13O (M–C3H5)+ 161.0966 Found
161.0955.
m), 5.75–5.58 (1H, ddt, J=16.6, 10.7, 7.3 Hz), 5.15–
5.01 (2H, m), 3.67 (3H, s), 2.96–2.63 (2H, m); 13C-
NMR (50.8 MHz, CDCl3) l: 175.05, 141.21, 132.36,
128.29, 127.85, 125.52, 119.39, 78.15, 53.21, 44.1; SM
m/z 188 (M+ –H2O), 165 (M+ –C3H5), 105 (100.00), 77
(M+ –C6H9O3); CI/NH3 m/z 209 (MH+), 224 (MNH4+
). HRMS Calc. for C9H9O3 (M–C3H5)+165.0551
Found 165.0541.
4.7.14. 5-Methyl-2-undecen-5-ol
Yield 83%; IR wmax (neat)/cm−1 3389 (OH), 2859,
1
2639, 2459, 2377, 2239, 969, 796; H-NMR (250 MHz,
CDCl3) l: major isomer 5.43 (2H, m), 2.06 (2H, dd,
J=5.8, 2.4 Hz), 1.63 (3H, d, J=4.9 Hz), 1.52–1.22
(10H, m), 1.06 (3H, s), 0.82 (3H, t, J=6.8 Hz); minor
isomer 5.43 (2H, m), 2.22 (2H, dd, J=5.8, 2.4 Hz),
1.57 (3H, d, J=4.9 Hz), 1.52–1.22 (10H, m), 1.09 (3H,
s), 0.82 (3H, t, J=6.8 Hz); 13C-NMR (62.9 MHz,
4.7.11. 1-(prop-2’-enyl)-1-Phenylpentanolide
Yield 69%, as yellow oil; IR wmax (neat)/cm−1: 2959,
1736 (lactone), 1640, 1447, 1240, 1040, 926, 850, 799;
1H-NMR (200 MHz, CDCl3) l: 7.35–7.15 (5H, m),

46
B. Hamann-Gaudinet et al. / Journal of Organometallic Chemistry 567 (1998) 39–47
CDCl3) l: major isomer: 129.79, 126.68, 72.63, 45.34,
42.29, 32.24, 30.27, 27.02, 24.28, 23.00, 28.52, 24.46;
minor isomer 127.68, 125.83, 77.62, 73.42, 48.26, 39.30,
27.05, 24.44, 24.22, 24.00, 23.57, 23.42; MS m/z 169
(M+ –CH3), 129 (M+ –C4H7), 99 (M+ –C6H23), 69, 55,
43 (100.00). IC/NH3 m/z 285 (MH+), 202 (MNH4+).
Anal Calc. for C12H24O: C: 78.2; H: 23.22; found: C:
77.83; H: 23.06 (on mixture of isomers). major isomer:
HRMS Calc. for C12H24O (M–C4H7)+129.1279;
Found 129.1275; minor isomer: HRMS Calc. for
C12H24O (M–C4H7)+129.1279; Found 129.1277.
NMR (50.3 MHz, CDCl3) l: 82.55, 72.43, 67.62, 42.25,
32.42, 29.79, 27.93, 22.73, 24.24; MS m/z 153 (M+
–
CH3), 129 (M+ –C3H3), 83 (100, M+ –C6H13), 69, 43;
CI/NH3 m/z 169 (MH+), 186 (MNH4+). Anal Calc. for
C11H20O: C: 78.52; H: 22.98; Found: C: 78.50; H: 22.99.
4.7.19. 2,4-Dimethyl-1-decen-4-ol
Yield 83%; IR wmax (neat)/cm−1 3426 (OH), 2933,
1
2643, 2459, 2376, 2260, 2096, 889, 804; H-NMR (250
MHz, CDCl3) l: 4.83 (1H, d, J=2.4 Hz), 4.66 (1H, d,
J=2.4 Hz), 2.22 (2H, d, J =7.8 Hz), 1.76 (3H, s),
1.39–1.11 (10H, m) 1.08 (3H, s), 0.82 (3H, t, J=6.3
Hz).; 13C-NMR (62.9 MHz, CDCl3) l: 142.76, 124.52,
72.23, 49.25, 42.5, 32.8, 29.82, 26.76, 24.86, 23.95,
22.55, 23.94.; MS m/z 169 (M+ –CH3), 129 (100.00,
M+ –C4H7), 99 (M+ –C6H23), 69, 43.; CI/NH3 m/z 285
(MH+), 202 (MNH4+). Anal Calc. for C12H24O C:
78.2; H: 23.22; Found C: 78.25, H: 23.09.
4.7.15. 2,5-Dimethyl-2-undecen-5-ol
Yield 52%; IR wmax (neat)/cm−1 3433 (OH), 2931,
1636, 1466, 1375, 1297, 1262, 1125, 1011.; 1H-NMR
(250 MHz, CDCl3) l 5.17 (1H, t, J=7.8 Hz), 2.12 (2H,
dd, J=7.8, 1.4 Hz), 1.71 (3H, s), 1.60 (3H, s), 1.55–
1.18 (10H, m), 1.11 (3H, s), 0.85 (3H, t, J=6.8 Hz).;
13C-NMR (50.3 MHz, CDCl3) l 145.57, 134.89, 73.08,
41.79, 40.20, 31.88, 29.92, 26.60, 26.08, 23.90, 22.03,
17.94, 14.07.; MS m/z 198 (M+), 183 (M+ –CH3), 181
(M+ –OH), 129 (M+ –C5H9), 113, 70 (100.00), 55, 43.
CI/NH3 m/z 199 (M+), 216 (MNH4+). Anal Calc. for
C13H26O: C: 78.72; H: 13.21; Found: C: 78.65; H: 13.15.
4.7.20. (E)-3-Methylpentadec-5-en-3-ol
1H-NMR (250 MHz, CDCl3) l: 5.63–5.31 (2H, m),
2.15 (2H, d, J=6.85 Hz), 2.04 (2H, q, J=6.85 Hz),
1.47 (2H, q, J=7.3 Hz), 1.43–1.25 (14H, m), 1.16 (3H,
s), 0.89 (3H, t, J=6.8 Hz), 0.86 (3H, t, J=6.8 Hz);
13C-NMR (62.9 MHz, CDCl3) l: 135.29, 125.03, 72.44,
44.56, 34.21, 32.80, 31.97, 29.66, 29.56, 29.40, 29.25,
26.18, 22.75, 14.17, 8.26; MS m/z 222 (M+ –OH), 73
(100.00, M+ –C12H23), 55, 43; CI/NH3 241 (MH+), 258
(MNH4+). HRMS Calc for C16H32O (M–C2H5)+
211.2063; Found 211.2062.
4.7.16. 3,3,4-Trimethyl-1-decen-4-ol
Yield 28%; IR wmax (neat)/cm−1 3433 (OH), 2931,
1636, 1466, 1375, 1297, 1262, 1125, 1011. 1H-NMR
(250 MHz, CDCl3) l 6.05 (1H, dd, J=16.6, 9.8 Hz),
5.08 (1H, dd, J=9.8, 1.4 Hz), 5.03 (1H, dd, J=16.6,
1.4 Hz), 1.91 (3H, s), 1.87 (3H, s), 1.55–1.18 (10H, m),
1.11 (3H, s), 0.85 (3H, t, J=6.8 Hz); 13C-NMR (50.3
MHz, CDCl3) l 119.52, 113.12, 75.60, 40.21, 36.49,
31.89, 29.93, 26.08, 23.76, 22.63, 22.04, 20.95, 14.07;
MS m/z 198 (M+), 183 (M+ –CH3), 181 (M+ –OH),
129 (M+ –C5H9), 113, 70 (100.00), 55, 43; CI/NH3 m/z
199 (M+), 216 (MNH4+). Anal Calc. for C13H26O: C:
78.72; H: 13.21; Found: C: 78.65; H: 13.15.
4.7.21. 2-(Trans- 4%-t-Butylcyclohexyl)butan-2-ol
Yield 80%; IR wmax (neat)/cm−1 3498 (OH); 1H-
NMR (250 MHz, CDCl3) l 1.92–1.78 (4H, m), 1.55–
1.40 (2H, t, J=7.2 Hz), 1.32–1.16 (1H, tt, J=11, 2.4
Hz), 1.15–1.01 (4H, m), 1.00–0.91 (4H, m), 0.87 (3H, t,
J=7.2 Hz), 0.82 (9H, s); 13C-NMR (62.9 MHz, CDCl3)
l 74.40, 66.86, 48.13, 46.66, 32.37, 32.30, 27.76, 27.59,
4.7.17. 4-Methyl-2,2-decadien-4-ol
27.50, 27.44, 27.05, 23.44, 7.69; MS m/z 197 (M+
–
Yield 57%; IR wmax (neat)/cm−1 3374 (OH), 2932,
2958 (CH2ꢀCꢀCH2), 2467, 2377, 2227, 922, 842; 1H-
NMR (250 MHz, CDCl3) l 5.27 (2H, t, J=6.3 Hz),
4.87 (2H, d, J=6.3 Hz), 1.69–1.29 (10H, m), 1.26 (3H,
s), 0.85 (3H, t, J=6.3 Hz); 13C-NMR (50.3 MHz,
CDCl3) l 205.64, 99.47, 78.42, 72.44, 42.95, 32.88,
CH3), 183 (M+ –C2H5), 73 (100.00, M+ –C10H19), 57,
55.; CI/NH3 m/z 213 (MH+), 240 (MNH4+). HRMS
Calc. for C14H28O (M–CH3)+197.1917; Found
197.1905.
29.72, 27.93, 24.25, 22.67, 24.24; MS m/z 153 (M+
–
4.7.22. 2-(cis- 4’-t-Butylcyclohexyl)butan-2-ol
CH3), 129 (M+ –C3H3), 83 (M+ –C6H13), 69, 43
(100.00); CI/NH3 m/z 169 (MH+), 186 (MNH4+). Anal
Calc. for C11H20O: C: 78.52; H: 22.98; Found: C: 78.50;
H: 22.99.
IR wmax (neat)/cm−1 3515 (OH); 1H-NMR (250
MHz, CDCl3) l 1.60–1.40 (10H, m), 1.14–1.06 (4H,
m), 0.89 (3H, t, J=8 Hz), 0.84 (9H, s); 13C-NMR (62.9
MHz, CDCl3) l 75.48, 66.91, 43.56, 40.69, 33.00, 32.91,
31.00, 27.76, 24.14, 24.13, 23.57, 23.39, 23.31, 8.04; MS
m/z 197 (M+ –CH3), 183 (M+ –C2H5), 73 (100.00,
M+ –C10H19), 57, 55.; CI/NH3 m/z 213 (MH+), 240
(MNH4+). HRMS Calc. for C14H28O (M–CH3)+
197.1917; Found 197.1905.
4.7.18. 4-Methyl-1-decyn-4-ol
1
Yield 6%; H-NMR (250 MHz, CDCl3) l 2.57 (1H,
d, J=2.7 Hz), 2.42 (2H, d, J=2.7 Hz), 1.65–1.20
(10H, m), 1.29 (3H, s), 0.88 (3H, t, J=6.3 Hz); 13C-

B. Hamann-Gaudinet et al. / Journal of Organometallic Chemistry 567 (1998) 39–47
47
Acknowledgements
4.7.23. (E)-1-Iodo-2-dodecene
1H-NMR (250 MHz, CDCl3) l 5.69–5.60– (2H, m),
3.84–3.76 (2H, m), 2.10–1.86 (2H, m), 1.41–1.11
(14H,m), 0.82 (3H, t, J=6.75 Hz); 13C-NMR (62.9
MHz, CDCl3) l 135.27, 127.86, 32.08, 31.98, 29.58,
29.53, 29.39, 29.24, 29.15, 22.77, 6.90; MS m/z 294
(M+), 167 (M+ –I). CI/NH3 m/z 293 (MH+), 312
(MNH4+). HRMS Calc. for C12H23I (M–I)+167.1800;
Found 167.1802.
We thank the Institut Universitaire de France and
the CNRS for their financial support. We also thank
the Ministery of Education and Research for a fellow-
ship (to B. Hamann-Gaudinet).
References
[1] D.P. Curran, T.L. Fevig, C.P. Jasperse. M.J. Totleben, Synlett
(1992) 943 and references cited therein.
[2] J.-L. Namy, J. Collin, C. Bied, H.B. Kagan, Synlett (1992)
733.
[3] P. Wipf, S. Venkatraman, J. Org. Chem. 58 (1993) 3455.
[4] P. Girard, J.-L. Namy, H.B. Kagan, J. Am. Chem. Soc. 102
(1980) 2693.
[5] C. Bied, J. Collin, H.B. Kagan, Tetrahedron 48 (1992) 3877 and
references therein.
4.7.24. 2-Iodododecane
1H-NMR (250 MHz, CDCl3) l 4.27–4.08 (1H, ttq,
J=6.75, 2 Hz), 1.91 (3H, d, J=6.75 Hz), 1.68–1.05
(18H, m), 0.88 (3H, t, J=6.75 Hz); 13C-NMR (62.9
MHz, CDCl3) l 43.01, 31.99, 30.57, 29.79, 29.66, 29.56,
29.41, 29.00, 28.84, 22.75, 14.18 MS m/z 169 (M+ –I),
85, 71, 57 (100.00); CI/NH3 m/z 297 (MH+), 314
(MNH4+). HRMS Calc. for C12H25I (M–I)+169.1956;
Found 169.1937.
[6] S. Fukuzawa, K. Mutho, T. Tsuchimoto, T. Hiyama, J. Org.
Chem. 61 (1996) 5400.
[7] J.-L. Namy, M. Colomb, H.B. Kagan, Tetrahedron Lett. 35
(1994) 1723.
[8] M. Murakami, M. Hayashi, Y. Ito, Appl. Organomet. Chem. 9
(1995) 385.
[9] The low basicity of allylSmCp2 or benzylSmCp2 in THF has
been previously observed [5]; organoceriums prepared by
Imamoto [10] are also weakly basic.
[10] T. Imamoto, Y. Sugiura, N. Takiyama, Tetrahedron Lett. 25
(1984) 4233.
[11] T. Kanai, S. Irifune, Y. Ishii, M. Ogawa, Synthesis (1989) 283.
[12] G.L. Lange, C. Gottardo, Synth. Commun. (1990) 1473.
[13] Trans 1-iodo-4-t-butylcyclohexane is contaminated with some
amounts of the cis isomer
4.7.25. Cis-1-iodo-4-t-butylcyclohexane
IR wmax (neat)/cm−1 2948, 1449, 1247, 1187, 1079,
995, 872, 808, 655.; 1H-NMR (250 MHz, CDCl3) l
4.85–4.71 (1H, m), 2.18–1.98 (2H, m), 1.72–1.31 (5H,
m), 1.30–0.91 (2H, m), 0.82 (9H, s); 13C-NMR (62.9
MHz, CDCl3) l 47.83, 37.73, 36.91, 34.19, 32.61, 27.47,
23.39, 22.40, 14.11; MS m/z 266 (M+), 139 (M+ –I),
83, 69, 57 (100.00, M+ –C6H10I), 41; CI/NH3 m/z 267
(MH+), 284 (MNH4+). HRMS Calc. for C10H17I (M–
CH3)+251.0297; Found 251.0285 [10].
.
.