(E)-dimethyl 2-oxopent-3-enylphosphonate: An excellent substrate for cross-metathesis-easy access to functionalized heterocycles

Article abstract of DOI:10.1002/ejoc.201101398

Simple and efficient access to tetrahydrofurans, tetrahydropyrans, and pyrrolidines through a tandem cross-metathesis/1,4-addition process from (E)-dimethyl 2-oxopent-3-enylphosphonate and N-protected ω-unsaturated amines or alcohols under microwave irrad

Full text of DOI:10.1002/ejoc.201101398

FULL PAPER
DOI: 10.1002/ejoc.201101398
(E)-Dimethyl 2-Oxopent-3-enylphosphonate: An Excellent Substrate for Cross-
Metathesis – Easy Access to Functionalized Heterocycles
Thomas Cochet,[a] Didier Roche,[b] Véronique Bellosta,*[a] and Janine Cossy*[a]
Keywords: Phosphorus / Heterocycles / Metathesis / Michael addition / Tandem reaction
Simple and efficient access to tetrahydrofurans, tetra- Grubbs–Hoveyda catalyst is highly chemoselective, a diver-
hydropyrans, and pyrrolidines through a tandem cross-me- sity of functionalized heterocycles were synthesized. Further-
tathesis/1,4-addition process from (E)-dimethyl 2-oxopent-3-
enylphosphonate and N-protected ω-unsaturated amines or
alcohols under microwave irradiation is described. As the
more, an additional functionalization can be performed due
to the presence of a side chain that possesses a ketophos-
phonate at the C2 position of the heterocycle.
Introduction
Nowadays, cross-metathesis (CM) is considered as an
atom economical reaction that allows the construction of
di- and trisubstituted C=C bonds under mild conditions.[1]
Due to the development of active and stable catalysts such
as [Ru]-I,[2] [Ru]-II,[3] [Ru]-III,[4] and [Ru]-IV[5] (Figure 1)
and due to the chemoselectivity of these catalysts, the olefin
partners can be substituted by a variety of functional
groups such as a hydroxy, a ketone, an ester, an amide, an
ether, or a protected amine. Furthermore, the ruthenium
catalysts, either by themselves or by in situ modification,
can induce tandem reactions.[6] One-pot sequential reac-
tions[7] can also take place due to the compatibility of the
ruthenium catalysts with other catalysts and/or reagents.[8]
During the past decade, some examples of tandem CM/
1,4-addition have been described. Hex-1-enols have been
coupled with enones to obtain tetrahydropyran skeletons by
using catalyst [Ru]-III.[9,10] It has also been reported that ω-
unsaturated protected amines,[11] sulfinylamines,[12] pyr-
roles,[13] and indoles[14] can be involved in a tandem CM/
aza-Michael sequence. However, in most cases the presence
of additives such as BF3·OEt2, Ti(OiPr)4, or phosphoric
acid was required to induce an aza-Michael reac-
tion.[11,12,14]
Figure 1. Ruthenium catalysts.
according to a tandem CM/1,4-addition without any addi-
tive (Scheme 1). It is worth noting that β-ketophosphonates
B and E can be involved in a Horner–Wadsworth–Emmons
reaction (HWE) for further functionalization to produce
unsymmetrical dienones C or heterocycles F that can be
useful precursors to synthesize a variety of products.
Results and Discussion
Here, we report that a CM can be performed between
γ,δ-unsaturated β-ketophosphonate 1 and functionalized
olefins A to produce enones B. Furthermore, heterocycles
of type E can be obtained from 1 and suitable olefins D,
The synthesis of the known phosphonate 1 was achieved,
according to the described literature procedure, by treat-
ment of dimethyl methylphosphonate (2 equiv.) with nBuLi
(2.2 equiv., THF, –78 °C) followed by the addition of (E)-
methyl but-2-enoate (1 equiv., –78 °C Ǟ r.t., 16 h).[15] The
resulting γ,δ-unsaturated β-ketophosphonate 1 was isolated
in 90–94% yield (Scheme 2).
The CM reaction involving 1 was performed with dif-
ferent ω-unsaturated alcohols and N-protected ω-unsatu-
rated amines. When but-3-en-1-ol (2a) (1 equiv.) was treated
with [Ru]-II (5 mol-%) at room temperature for 16 h in the
[a] Laboratoire de Chimie Organique, ESPCI ParisTech
CNRS UMR 7084
10 rue Vauquelin, 75231 Paris Cedex 05, France
Fax: +33-1-40794660
E-mail: veronique.bellosta@espci.fr
janine.cossy@espci.fr
[b] Edelris s.a.s.
115, Avenue Lacassagne, 69003 Lyon, France
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201101398.
Eur. J. Org. Chem. 2012, 801–809
© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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T. Cochet, D. Roche, V. Bellosta, J. Cossy
FULL PAPER
Scheme 1. General scheme.
the amount of 1 to 3 equiv. and performing the reaction at
room temperature for 16 h furnished 3a in 75% yield
(Table 1, Entry 4). Under these latter conditions, substi-
tuted butenol 2b was converted into 3b in 14% yield and
no trace amounts of CM product 3c were observed from
1-phenyl-but-3-enol (2c) (Table 1, Entries 5 and 6). These
conditions furnished cross-metathesis product 3d in only
15% yield from monoprotected diol 2d; however, when the
CM between 1 and 2d was performed under microwave irra-
diation (100 °C, 2ϫ15 min) and after two consecutive ad-
ditions of 5 mol-% of [Ru]-III catalyst,[16] 3d was isolated in
53% yield (Table 1, Entries 7 and 8). It is worth noting that
when the CM was performed between 1 and 1-methyl- or
1-phenylprop-2-en-1-ol, only homodimers of the allylic
alcohols were formed, even under microwave irradiation.
When a CM was achieved between pent-1-en-5-ol (4a)
and 1 in the presence of [Ru]-III (5 mol-%) in CH2Cl2 at
room temperature for 16 h (conditions A), 5a was isolated
in only 15% yield (Table 2, Entry 1). By forcing the condi-
tions, for example, by performing the reaction at 100 °C
under microwave irradiation for 30 min with two successive
additions of [Ru]-III (2ϫ5 mol-%) every 15 min (condi-
tions B), functionalized tetrahydrofuran 6a was isolated in
54% yield (Table 2, Entry 2). The formation of this product
can be explained by a CM/oxa-Michael cascade sequence,
probably due to the activation of the unsaturated ketone
either by the ruthenium intermediate [Ru]-IIIЈ,[11] which can
act as a Lewis acid, or by a ruthenium hydride species re-
sulting from the thermal decomposition of [Ru]-IIIЈ
(Scheme 3).[9,17] This cascade reaction is general, as 6b and
6c were formed from 4b and 4c, respectively, in good yields
(77% to quant.); however, the diastereoselectivity was poor
(dr ≈ 1:1–1.5:1; Table 2, Entries 3 and 4). As for but-3-en-1-
ol (4a), when hex-5-en-1-ol (4d) was engaged in a CM, the
obtained products were enone 5d (20%) under conditions A
and tetrahydropyran 6d (46%) under conditions B (Table 2,
Entries 5 and 6). Thus, when α-substituted hexenols 4e and
4f (Table 2, Entries 7 and 8) were engaged in a CM under
conditions B, the corresponding disubstituted tetrahydropy-
rans 6e and 6f were isolated in excellent yield (90% and
80%) with excellent diastereoselectivities (Ͼ98:2) in favor
of the cis-isomers.
Scheme 2. Preparation of 1.
presence of 1 (3 equiv.), CM product 3a was obtained in
10% yield (Table 1, Entry 1). Increasing the amount of cat-
alyst to 10 mol-% and heating the reaction at 40 °C allowed
the isolation of 3a in 70% yield (Table 1, Entry 2). When a
stoichiometric amount of 1 and 2a was treated with [Ru]-
III (5 mol-%) at room temperature for 16 h only trace
amounts of 3a were observed (Table 1, Entry 3). Increasing
Table 1. CM with homoallyllic alcohols.
As the ruthenium catalyst [Ru]-III can induce a CM/1,4-
addition cascade, the reactivity of ω-unsaturated N-pro-
tected amines 7a–g was examined to synthesize function-
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Easy Access to Functionalized Heterocycles
Table 2. CM with pent-4-en-1-ols and hex-5-en-1-ols.
alized pyrrolidines and piperidines. When ω-unsaturated
tert-butylcarbamates such as 7a and 7b were involved in a
CM reaction with 1 {[Ru]-III (2ϫ5 mol-%), CH2Cl2,
100 °C, μW, 2 ϫ15 min}, they were converted into pyrroli-
dines 9a and 9b, respectively, in moderate yields and selec-
tivities (65–43%; dr = 70:30; Table 3, Entries 1 and 2).
When ω-unsaturated N-tosylamine 7c was involved in CM
with 1, pyrrolidine 9c was isolated in 55% yield and substi-
tuted N-tosylamine 7d was converted into 9d (60%) with a
good diastereomeric ratio of 80:20 (Table 3, Entries 3 and
4). Again, the overall process was efficient and provided
substituted pyrrolidines in good yields with good diastereo-
selectivities. Unfortunately, when N-tosyl-hex-5-enamines
7e–g were used, only CM products 8e–g were obtained in
good yield (72–88%) and no trace amounts of the corre-
sponding cyclized products were detected (Table 3, En-
tries 5–7).
Table 3. CM with unsaturated N-protected amines.
Scheme 3. Possible catalysts for the 1,4-addition.
Eur. J. Org. Chem. 2012, 801–809
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803

T. Cochet, D. Roche, V. Bellosta, J. Cossy
FULL PAPER
It is worth noting that for compound 7h (Scheme 4),
pyrrolidine 9h was formed but, as its polarity was similar
to that of phosphonate 1, 9h could not be separated from
the excess amount of phosphonate 1 (Scheme 4). In order
to achieve the purification of 9h, a HWE reaction was per-
formed on the mixture of 1/CM product by using benzalde-
hyde. Thus, 7h was engaged in the CM/1,4-addition cascade
and after chromatography on silica gel, the isolated mixture,
constituted by 1 and 9h, was engaged in a HWE reaction
to produce enone 10h in 80% yield from 7h over the two-
Experimental Section
General Remarks: Infrared (IR) spectra were recorded with a
Bruker Tensortm 27 (IRFT) on an ATR plate. NMR was per-
formed with a Bruker Avance-1 400 instrument. H NMR spectra
1
were recorded at 400 MHz in CDCl3 and data are reported as fol-
lows: chemical shift in ppm from tetramethylsilane as an internal
standard, multiplicity (s = singlet, d = doublet, t = triplet, q =
quartet, quint. = quintuplet, m = multiplet or overlap of non-equiv-
alent resonances, br. = broad), integration. 13C NMR spectra were
recorded at 100 MHz in CDCl3 and data are reported as follows:
chemical shift in ppm from tetramethylsilane with the solvent as
an internal indicator (CDCl3, δ = 77.16 ppm), multiplicity, with
respect to proton (deduced from DEPT experiments, s = quater-
nary C, d = CH, t = CH2, q = CH3). High-resolution mass spectra
(HRMS) were performed by the Groupe de Spectrométrie de
Masse de lЈUniversité Pierre et Marie Curie (Paris-France). Optical
rotations were measured with a Perkin–Elmer model 343 polarime-
ter with a 1-dm path length. TLC was performed on Merck 60F254
silica gel plates with UV and Hanessian stain or para-anisaldehyde.
CH2Cl2 was distilled from CaH2, and Et2O and THF were distilled
from sodium/benzophenone. Phosphonate 1[15] and olefins 2c,[20]
4b,[21] 4c,[22] 4e,[21] 4f,[23] 7a,[22] 7c,[22] 7d,[24] 7e,[25] 7f,[26] 7g,[26] 7h,[27]
and 7i[28] were obtained following existing procedures. Other rea-
gents were obtained from commercial suppliers and used as re-
ceived. Flash column chromatography was performed on silica gel
(230–400 mesh). Diastereomeric ratios were measured by examina-
step sequence (Scheme 4). Compound 10h can be diastereo-
[18]
selectively reduced by using LiAlH(OtBu)3
to produce
hydroxypyrrolidine 11, which can be a useful building block
to access natural products and/or biologically active com-
pounds.[19]
1
tion of the H NMR spectrum of the crude material. All reactions
were performed under an argon atmosphere.
General Procedure for CM Reactions
Method A: To a solution of phosphonate 1 (117 mg, 0.6 mmol,
3 equiv.) and olefin (0.2 mmol, 1 equiv.), in anhydrous CH2Cl2
(1.5 mL) at room temperature was added catalyst [Ru]-II (6 mg,
5 mol-%) or [Ru]-III (6 mg, 5 mol-%) in one portion. After 16 h at
room temperature, the reaction mixture was evaporated and puri-
fied by flash chromatography on silica gel to afford the title com-
pound. In some cases, a second purification by medium-pressure
liquid chromatography (MPLC, AcOEt) was required to separate
the products.
Method B: To a solution of phosphonate 1 (117 mg, 0.6 mmol,
3 equiv.) and olefin (0.2 mmol, 1 equiv.) in anhydrous CH2Cl2
(1.5 mL), in a microwave vial at room temperature was added cata-
lyst [Ru]-III (6 mg, 5 mol-%) in one portion. The vial was sealed
and heated under microwave irradiation. After 15 min at 100 °C, a
second portion of [Ru]-III (6 mg, 5 mol-%) was added, and the re-
action was heated for 15 min at 100 °C. Evaporation of the volatiles
and purification by flash chromatography afforded the title com-
pound. In some cases, a second purification by medium-pressure
liquid chromatography (MPLC, AcOEt) was required to separate
the products.
Scheme 4. CM with ω-unsaturated carbamates.
ω-Unsaturated carbamate 7i was also engaged in this
two-step process. As for N-tosyl-hex-5-enamines, the forma-
tion of the desired piperidine was not observed and the CM
product was the only product formed that gave, after a
HWE reaction, unsymmetrical divinyl ketone 10i in 73%
yield.
Method C: To a solution of phosphonate 1 (117 mg, 0.6 mmol,
3 equiv.) and olefin (0.2 mmol, 1 equiv.) in anhydrous CH2Cl2
(1 mL) at room temperature was added catalyst [Ru]-II (12 mg,
10 mol-%) in one portion. After 4 h at 40 °C, the reaction mixture
Conclusions
In summary, we have developed a CM reaction involving
γ,δ-unsaturated β-ketophosphonate 1 catalyzed by [Ru]-III. was evaporated and purified by flash chromatography on silica gel
to afford the title compound.
Depending on the olefinic partners and conditions, a CM/
1,4-addition sequence can take place without any additives
to furnish functionalized tetrahydrofurans, tetrahydropy-
rans, and pyrrolidines. These functionalized heterocycles
are interesting building blocks that can be involved in the
synthesis of natural products and/or bioactive compounds.
(3S,4R)-4-Triethylsilyloxypent-1-en-3-ol and (3R,4R)-4-Triethylsil-
yloxypent-1-en-3-ol (2d): To a solution of (R)-isobutyl lactate
(7.02 g, 48 mmol, 1 equiv.) in DMF (50 mL) at room temperature
was added imidazole (3.88 g, 57 mmol, 1.2 equiv.) and TESCl
(8.5 mL, 50 mmol, 1.1 equiv.). After 1.5 h of stirring, the reaction
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Easy Access to Functionalized Heterocycles
was quenched with H2O (20 mL). The aqueous layer was extracted
with Et2O (4ϫ50 mL), and the combined organic layers were dried
with MgSO4, filtered, and concentrated under reduced pressure to
afford isobutyl (2R)-2-(triethylsilyloxy)propionate (2d-1; 12.48 g,
47.8 mmol) as a colorless oil. Yield: 99%. [α]2D0 = +25.3 (c = 0.04,
Dimethyl [(E)-6-Hydroxy-2-oxohex-3-en-1-yl]phosphonate (3a)
Method A: But-3-en-1-ol (2a; 14 mg, 0.2 mmol, 1 equiv.), phos-
phonate 1 (117 mg, 0.6 mmol, 3 equiv.), and [Ru]-II (6 mg, 5 mol-
%) led to 3a (5 mg, 0.024 mmol) after purification on silica gel
(AcOEt to AcOEt/MeOH = 95:5), as a brown oil. Yield: 10%.
CHCl ). IR: ν = 2957, 2878, 2360, 2341, 1757, 1459, 1143,
˜
3
Method A: But-3-en-1-ol (2a; 14 mg, 0.2 mmol, 1 equiv.), phos-
phonate 1 (117 mg, 0.6 mmol, 3 equiv.), and [Ru]-III (6 mg, 5 mol-
%) led to 3a (34 mg, 0.15 mmol) after purification on silica gel (Ac-
OEt to AcOEt/MeOH = 95:5) as a brown oil. Yield: 75%.
1002 cm–1. H NMR (400 MHz, CDCl3): δ = 4.34 (q, J = 6.7 Hz,
1
1 H), 3.90 (ddsystAB, J = 10.4, 6.8 Hz, 1 H), 3.86 (ddsystAB, J = 10.4,
6.7 Hz, 1 H), 1.96 (nonupletapp, J = 6.8 Hz, 1 H), 1.41 (d, J =
6.7 Hz, 3 H), 0.99 (m, 15 H), 0.63 (q, J = 7.8 Hz, 6 H) ppm. 13C
NMR (100 MHz, CDCl3): δ = 174.1 (s), 70.8 (t), 68.1 (d), 27.7 (d),
21.5 (q), 19.0 (q, 2 C), 6.6 (q, 3 C), 4.6 (t, 3 C) ppm. MS (EI): m/z
(%) = 246 (1) [M – Me]+, 217 (100), 189 (86), 161 (48), 133 (23),
105 (26), 94 (14), 80 (25), 66 (27), 59 (20). HRMS (ESI): calcd. for
C13H28O3NaSi [M + Na]+ 283.1700 found 283.1692. To a solution
of 2d-1 (2.6 g, 10 mmol, 1 equiv.) in anhydrous Et2O (40 mL) at
–78 °C was added DIBAL-H (1 m in hexanes, 15 mL, 15 mmol,
1.5 equiv.), and the reaction mixture was warmed to room tempera-
ture. After 1.5 h, the reaction was quenched with H2O (20 mL),
and the precipitate was dissolved in Et2O (20 mL). The aqueous
layer was then extracted with Et2O (3ϫ30 mL), and the combined
organic layers were dried with MgSO4, filtered, and concentrated
under vacuum. Purification by flash chromatography (PE to PE/
Et2O = 10:1) afforded (2R)-2-triethylsilyloxypropionaldehyde (2d-
2; 1.35 g, 7.2 mmol) as a colorless oil. Yield: 72%. Spectral data
match those previously described in the literature for (2S)-2d-2.[29]
[α]2D0 = +10 (c = 1.56, CHCl3) {ref.[29] for ent-2d-2: [α]2D0 = –11.5 (c
Method C: But-3-en-1-ol (2a; 14 mg, 0.2 mmol, 1 equiv.), phos-
phonate 1 (117 mg, 0.6 mmol, 3 equiv.), and [Ru]-II (6 mg, 5 mol-
%) led to 3a (22 mg, 0.10 mmol) after purification on silica gel (Ac-
OEt to AcOEt/MeOH = 95:5) as a brown oil. Yield: 70%. IR: ν =
˜
3378, 2853, 1691, 1663, 1624, 1447, 1406, 1239, 1183, 1020 cm–1.
1H NMR (400 MHz, CDCl3): δ = 6.94 (dt, J = 16.0, 7.2 Hz, 1 H),
6.23 (br. d, J = 16.0 Hz,1 H), 3.76 (tapp, J = 6.0 Hz, 2 H), 3.73 (d,
2
3JH,P = 11.3 Hz, 6 H), 3.12 (d, JH,P = 22.6 Hz, 2 H), 3.00 (br. s, 1
H), 2.46 (br. qapp, J = 6.5 Hz, 2 H) ppm. 13C NMR (100 MHz,
2
CDCl3): δ = 191.0 (s, JC,P = 6.0 Hz), 148.2 (d), 131.8 (d), 60.6 (t),
2
1
53.1 (q, JC,P = 6.8 Hz, 2 C), 38.8 (t, JC,P = 128.3 Hz), 35.9 (t)
ppm. HRMS (ESI): calcd. for C8H15O5PNa [M + Na]+ 245.0549;
found 245.0542.
Dimethyl [(E)-6-Hydroxy-2-oxohept-3-enyl]phosphonate (3b): Ac-
cording to method A, 1-phenylbut-3-enol (2b; 30 mg, 0.2 mmol,
1 equiv.), phosphonate 1 (117 mg, 0.6 mmol, 3 equiv.), and [Ru]-III
(6 mg, 5 mol-%) led to 3b (6.6 mg, 0.028 mmol) after purification
on silica gel (AcOEt to AcOEt/MeOH = 95:5) as a brown oil.
= 1.55, CHCl )}. IR: ν = 2957, 2878, 1739, 1459, 1415, 1375, 1240,
˜
3
1134, 1096, 1007 cm–1. H NMR (400 MHz, CDCl3): δ = 9.63 (d,
1
Yield: 14%. IR: ν = 3408, 2961, 2925, 2854, 1691, 1667, 1626, 1251,
˜
1
1029 cm–1. H NMR (400 MHz, CDCl3): δ = 7.97 (ddd, J = 16.0,
J = 1.6 Hz, 1 H), 4.09 (qd, J = 6.8, 1.6 Hz, 1 H), 1.29 (d, J =
6.8 Hz, 3 H), 0.98 (t, J = 7.9 Hz, 9 H), 0.64 (q, J = 7.9 Hz, 6 H)
ppm. 13C NMR (100 MHz, CDCl3): δ = 204.3 (s), 73.5 (d), 18.6
(q), 6.7 (q, 3 C), 4.7 (t, 3 C) ppm. MS (EI): m/z (%) = 189 (1), 159
(76), 132 (11), 131 (100), 129 (11), 115 (46), 113 (13), 103 (29), 101
(19), 87 (69), 75 (23), 59 (38), 58 (12), 57 (11). HRMS (ESI): calcd.
for C10H24O3NaSi [M + Na + MeOH]+ 243.1387; found 243.1388.
To a solution of vinylmagnesium chloride (1.6 m in THF, 4 mL,
6.4 mmol, 1.2 equiv.) in anhydrous THF (7.5 mL) at –60 °C was
added a solution of 2d-2 (1 g, 5.3 mmol, 1 equiv.) in THF (7.5 mL)
by cannula, and the reaction was warmed to room temperature.
After 2 h the reaction was quenched with aqueous saturated NH4Cl
(10 mL) and H2O was added (10 mL). The aqueous layer was ex-
tracted with Et2O (3ϫ40 mL), and the combined organic layers
were dried with MgSO4, filtered, and concentrated under vacuum
to afford 2d (0.92 g, 4.2 mmol) as a mixture of syn/anti-diastereo-
7.6, 6.8 Hz, 1 H), 6.19 (dtapp, J = 5.9, 1.4 Hz, 1 H), 3.99 (sext.app
,
=
,
3
3
J = 5.9 Hz, 1 H), 3.75 (d, JH,P = 11.2 Hz, 3 H), 3.74 (d, JH,P
2
1
11.2 Hz, 3 H), 3.26 (tapp, JH,P = JH,P = 22.8 Hz, 1 H), 3.22 (tapp
2JH,P
=
1JH,P = 22.8 Hz, 1 H), 2.47–2.28 (m, 3 H), 1.24 (d, J =
6.0 Hz, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 191.2 (s, 2JC,P
2
= 6.0 Hz), 148.2 (d), 132.5 (d), 67.0 (d), 53.4 (q, JC,P = 7.0 Hz, 2
C), 42.6 (t), 39.3 (t, 1JC,P = 127.4 Hz), 23.4 (q) ppm. HRMS (ESI):
calcd. for C9H17O5PNa [M + Na]+ 259.0706; found 259.0701.
Dimethyl [(E)-(5S,6R)-5-Hydroxy-2-oxo-6-(tert-butyldimethyl-silyl-
oxy)hept-3-enyl]phosphonate (3d)
Method A: Alcohol 2d (43 mg, 0.2 mmol, 1 equiv.), phosphonate 1
(117 mg, 0.6 mmol, 3 equiv.), and [Ru]-III (12 mg, 10 mol-%) led to
3d (6 mg, 0.03 mmol) after purification on silica gel (EP/AcOEt =
40:60) as a brown oil. Yield: 15%.
isomers in a 1:4 ratio. Yield: 80%. IR: ν = 3445, 2955, 2877, 1458,
Method B: Alcohol 2d (43 mg, 0.2 mmol, 1 equiv.), phosphonate 1
(117 mg, 0.6 mmol, 3 equiv.), and [Ru]-III (2ϫ6 mg, 2ϫ5 mol-%)
led to 3d (39 mg, 0.11 mmol) after purification on silica gel (EP/
˜
1415, 1378, 1238, 1129, 1088, 1003 cm–1. 1H NMR (400 MHz,
CDCl3, anti diastereoisomer): δ = 5.75 (br. ddd, J = 17.3, 10.6,
6.0 Hz, 1 H), 5.23 (dt, J = 17.5, 1.6 Hz, 1 H), 5.12 (dt, J = 10.7,
1.6 Hz, 1 H), 3.98 (m, 1 H), 3.79 (qd, J = 6.4, 3.6 Hz, 1 H), 2.27
(br. s, 1 H), 1.02 (d, J = 6.3 Hz, 3 H), 0.90 (t, J = 7.9 Hz, 9 H),
0.55 (q, J = 7.6 Hz, 6 H) ppm. 13C NMR (100 MHz, CDCl3, anti
diastereoisomer): δ = 136.8 (d), 116.6 (t), 76.9 (d), 71.3 (d), 17.7
(q), 7.0 (q, 3 C), 5.2 (t, 3 C) ppm. 1H NMR (400 MHz, CDCl3,
syn diastereoisomer): δ = 5.75 (br. ddd, J = 17.3, 10.6, 6.0 Hz, 1
H), 5.23 (dt, J = 17.5, 1.6 Hz, 1 H), 5.12 (dt, J = 10.7, 1.6 Hz, 1
H), 3.73 (m, 1 H), 3.61 (quint.app, J = 6.2 Hz, 1 H), 2.58 (br. s, 1
H), 1.09 (d, J = 6.2 Hz, 3 H), 0.90 (t, J = 7.9 Hz, 9 H), 0.55 (q, J
= 8.0 Hz, 6 H) ppm. 13C NMR (100 MHz, CDCl3, syn): δ = 137.7
(d), 117.1 (t), 77.2 (d), 71.9 (d), 20.2 (q), 7.0 (q, 3 C), 5.2 (t, 3 C)
ppm. MS (EI): m/z (%) = 187 (85) [M – Et]+, 169 (10), 159 (67),
115 (72), 103 (100), 87 (55), 75 (62), 59 (21). HRMS (ESI): calcd.
for C11H24O2NaSi [M + Na]+ 239.1438; found 239.1438.
AcOEt = 40:60) as a brown oil. Yield: 53% IR: ν = 3372, 2956,
˜
2919, 2877, 2359, 1693, 1667, 1629, 1459, 1413, 1377, 1242,
1031 cm–1. 1H NMR (400 MHz, CDCl3): δ = 6.84 (dd, J = 15.8,
4.5 Hz, 1 H), 6.48 (dd, J = 15.8, 1.5 Hz, 1 H), 4.29 (br. tdapp, J =
6.2, 3.9 Hz, 1 H), 3.96 (dq, J = 6.2, 3.9 Hz, 1 H), 3.77 (d, J =
11.3 Hz, 6 H), 3.23 (d, J = 22.0 Hz, 2 H), 2.60 (m, 1 H), 1.10 (d, J
= 6.3 Hz, 3 H), 0.96 (t, J = 7.9 Hz, 9 H), 0.61 (q, J = 7 Hz, 6 H)
2
ppm. 13C NMR (100 MHz, CDCl3): δ = 190.8 (s, JC,P = 7.0 Hz),
2
146.6 (d), 129.2 (d), 75.0 (d), 70.5 (d) 53.1 (q, JC,P = 6.0 Hz, 2 C),
1
39.7 (t, JC,P = 128.8 Hz), 17.9 (q), 6.7 (q, 3 C), 4.9 (t, 3 C) ppm.
MS (EI): m/z (%) = 322 (1), 304 (100), 303 (79), 289 (13), 158
(13). HRMS (ESI): calcd. for C15H31O6PSiNa [M + Na]+ 389.1520;
found 389.1523.
Dimethyl [(E)-7-Hydroxy-2-oxohept-3-en-1-yl]phosphonate (5a): Ac-
cording to method A, alcohol 4a (17 mg, 0.2 mmol, 1 equiv.), phos-
Eur. J. Org. Chem. 2012, 801–809
© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
805

T. Cochet, D. Roche, V. Bellosta, J. Cossy
FULL PAPER
phonate 1 (117 mg, 0.6 mmol, 3 equiv.), and [Ru]-III (6 mg, 5 mol-
%) led to 5a (7 mg, 0.03 mmol) after purification on silica gel (Ac-
127.0 Hz), 34.0 (t), 31.4 (t) ppm. 1H NMR (400 MHz, CDCl3,
minor diastereomer): δ = 7.34–7.21 (m, 5 H), 5.02 (dd, 3J = 8.4,
3
OEt to AcOEt/MeOH = 90:10) as a brown oil. Yield: 15%. IR: ν
6.4 Hz, 1 H), 4.61 (m, 1 H), 3.79 (d, JH,P = 11.2 Hz, 3 H), 3.78
˜
3
2
= 3417, 2957, 2923, 1715, 1692, 1665, 1625, 1449, 1406, 1250,
(d, JH,P = 11.2 Hz, 3 H), 3.29–3.15 (m, 2 H), 3.02 (ddsystAB, J =
1
1029 cm–1. H NMR (400 MHz, CDCl3): δ = 6.95 (m, 1 H), 6.24 16.0, 7.2 Hz, 1 H), 2.83 (ddsystAB
,
2J = 16.0, 5.6 Hz, 1 H), 2.42–
(m, 1 H), 3.75 (m, 6 H), 3.66 (br. t, J = 6.4 Hz, 2 H), 3.20 (d, 2JH,P 2.16 (m, 4 H) ppm. 13C NMR (100 MHz, CDCl3, minor dia-
2
= 22.8 Hz, 2 H), 2.35 (br. qapp, J = 7.3 Hz, 2 H), 1.75 (m, 3 H) stereomer): δ = 200.5 (s, JC,P = 6.4 Hz), 143.3 (s), 128.3 (d, 2 C),
ppm. 13C NMR (100 MHz, CDCl3): δ = 191.0 (s), 150.1 (d), 130.4
(d), 61.9 (t), 53.1 (q, 2JC,P = 6.3 Hz, 2 C), 39.2 (t, 1JC,P = 129.0 Hz),
30.9 (t), 29.2 (t) ppm. MS (EI): m/z (%) = 193 (22), 166 (19), 151
(63), 127 (11), 126 (67), 124 (100), 119 (18), 111 (44), 109 (68), 95
(10), 94 (76), 85 (23), 79 (53), 71 (62), 55 (12). HRMS (ESI): calcd.
for C9H17O5NaP [M + Na]+ 259.0706; found 259.0711.
127.2 (d), 125.5 (d, 2 C), 80.5 (d), 75.6 (d), 53.1 (q, JC,P = 5.9 Hz,
2
1
2 C), 50.5 (t), 42.1 (t, JC,P = 127.0 Hz), 35.0 (t), 32.4 (t) ppm. MS
(EI, diastereomer one): m/z (%) = 208 (73), 193 (22), 166 (27), 151
(100), 129 (26), 124 (89), 117 (26), 111 (23), 109 (69), 105 (25), 94
(43), 91 (68), 77 (51), 55 (17). MS (EI, diastereomer two): m/z (%)
= 208 (4), 194 (12), 193 (65), 151 (100), 135 (23), 124 (48), 109 (59),
105 (42), 95 (21), 94 (55), 91 (65), 79 (41), 77 (45). HRMS (ESI):
calcd. for C15H21O5PNa [M + Na]+ 335.1019; found 335.1008.
Dimethyl [(E)-8-Hydroxy-2-oxooct-3-en-1-yl]phosphonate (5d): Ac-
cording to method A, alcohol 4d (20 mg, 0.2 mmol, 3 equiv.), phos-
phonate 1 (117 mg, 0.6 mmol, 3 equiv.), and [Ru]-III (6 mg, 5 mol-
%) led to 5d (10 mg, 0.4 mmol) after purification on silica gel (Ac-
OEt to AcOEt/MeOH = 90:10) as a brown oil slightly polluted by
Dimethyl
[2-Oxo-3-(5-pentyltetrahydrofuran-2-yl)propyl]phos-
phonate (6c): According to method B, alcohol 4c (31 mg, 0.2 mmol,
3 equiv.), phosphonate 1 (117 mg, 0.6 mmol, 3 equiv.), and [Ru]-III
(2ϫ6 mg, 2ϫ5 mol-%) led to 6c (47 mg, 0.15 mmol) after purifica-
tion on silica gel (AcOEt) followed by MPLC (AcOEt/MeOH =
the cyclic product. Yield: 20%. IR: ν = 3421, 2925, 2854, 1716,
˜
1691, 1664, 1625, 1457, 1405, 1250, 1028 cm–1. 1H NMR
(400 MHz, CDCl3): δ = 6.95 (dt, J = 16.0, 6.8 Hz, 1 H), 6.24 (br.
99:1) as a brown oil. Yield: 77%. IR: ν = 2956, 2929, 2857, 1714,
˜
3
dt, J = 16.0, 1.4 Hz, 1 H), 3.78 (d, JH,P = 11.2 Hz, 6 H), 3.65 (br.
1461, 1377, 1257, 1186, 1029 cm–1. 1H NMR (400 MHz, CDCl3,
2
t, J = 5.6 Hz, 2 H), 3.22 (d, JH,P = 22.4 Hz, 2 H), 2.34–2.24 (m, 2 equimolar mixture of cis/trans diastereoisomers):
δ = 4.34
H), 1.63–1.58 (m, 4 H) ppm. 13C NMR (100 MHz, CDCl3): δ = (quint.app, J = 7.0 Hz, 0.5 H), 4.20 (quint.app, J = 7.0 Hz, 0.5 H),
2
3
191.1 (s), 150.6 (d), 130.4 (d), 62.4 (t), 53.2 (q, JC,P = 6.7 Hz, 2
3.94 (quint.app, J = 7.0 Hz, 0.5 H), 3.79 (d, JH,P = 11.2 Hz, 6 H),
1
C), 39.3 (t, JC,P = 129.0 Hz), 32.4 (t), 32.1 (t), 29.2 (t) ppm. MS
3.79 (m, 0.5 H), 3.28–3.10 (m, 2 H), 2.89 (ddsystAB, J = 16.0, 7.0 Hz,
(EI): m/z (%) = 232 (5), 166 (20), 151 (83), 140 (87), 135 (12), 125 1 H), 2.75 (ddsystAB, J = 16.0, 5.6 Hz, 0.5 H), 2.72 (ddsystAB, J =
(52), 124 (100), 122 (10), 119 (19), 111 (16), 109 (76), 99 (22), 98
16.0, 5.8 Hz, 0.5 H), 2.18–1.91 (m, 2 H), 1.62–1.20 (m, 10 H), 0.88
(13), 95 (11), 94 (67), 93 (11), 85 (27), 79 (47), 67 (18), 57 (21), 55 (m, 3 H) ppm. 13C NMR (100 MHz, CDCl3, equimolar mixture of
(33). HRMS (ESI): calcd. for C10H19O5PNa [M + Na]+ 273.0862;
found 273.0861.
cis/trans diastereoisomers): δ = 201.0, 200.9 (s, JC,P = 6.8 Hz),
2
3
80.1, 79.3 (d), 74.9, 74.4 (d), 53.2 (q, JC,P = 12.7 Hz, 2 C), 50.5,
50.3 (t, 2 C), 42.1 (t, 1JC,P = 127.0 Hz), 36.2, 36.0 (t), 32.4, 32.1 (t),
31.9 (t), 31.4, 31.0 (t), 26.0 (t), 22.8 (t), 14.2 (q) ppm. MS (EI): m/z
(%) = 235 (47) [M – C5H11]+, 208 (56), 193 (27), 189 (11), 167 (20),
166 (25), 151 (100), 124 (34), 109 (37), 94 (16), 79 (15), 55 (19).
HRMS (ESI): calcd. for C14H27O5PNa [M + Na]+ 329.1488; found
329.1477.
Dimethyl [2-Oxo-3-(tetrahydrofuran-2-yl)propyl]phosphonate (6a):
According to method B, alcohol 4a (17 mg, 0.2 mmol, 1 equiv.),
phosphonate
1 (117 mg, 0.6 mmol, 3 equiv.), and [Ru]-III
(2ϫ6 mg, 2ϫ5 mol-%) led to 6a (25 mg, 0.11 mmol) after purifica-
tion on silica gel (AcOEt to AcOEt/MeOH = 90:10) as a brown
oil. Yield: 54%. IR: ν = 2956, 2926, 2855, 1714, 1462, 1385, 1253,
˜
1185, 1025 cm–1. H NMR (400 MHz, CDCl3): δ = 4.23 (m, 1 H), Dimethyl [2-Oxo-3-(tetrahydro-2H-pyran-2-yl)propyl]phosphonate
1
3.86 (m, 1 H), 3.81–3.67 (m, 7 H), 3.25–3.08 (m, 2 H), 2.88
(6d): According to method B, alcohol 4d (20 mg, 0.2 mmol,
3 equiv.), phosphonate 1 (117 mg, 0.6 mmol, 3 equiv.), and [Ru]-III
(ddsystAB, J = 16.1, 7.4 Hz,1 H), 2.77 (ddsystAB, J = 16.1, 5.4 Hz, 1
H), 2.10 (m, 1 H), 1.96–1.83 (m, 2 H), 1.50 (m, 1 H) ppm. 13C (2ϫ6 mg, 2ϫ5 mol-%) led to 6d (23 mg, 0.09 mmol) after purifica-
NMR (100 MHz, CDCl3): δ = 200.5 (s), 74.8 (d), 66.0 (t), 53.1 (q, tion on silica gel (AcOEt to AcOEt/MeOH = 90:10) as a brown
1
2JC,P = 6.0 Hz, 2 C), 49.8 (t), 42.0 (t, JC,P = 128.2 Hz), 31.5 (t),
oil. Yield: 46%. IR: ν = 2935, 2856, 1714, 1456, 1403, 1253,
˜
25.5 (t) ppm. MS (EI): m/z (%) = 218 (1), 193 (18), 166 (17), 151 1026 cm–1. H NMR (400 MHz, CDCl3): δ = 3.90 (m, 1 H), 3.82–
1
(68), 126 (69), 124 (100), 119 (16), 111 (53), 109 (67), 94 (76), 85
3.70 (m, 7 H), 3.44 (m, 1 H), 3.28–3.01 (m, 2 H), 2.92–2.59 (m, 2
(24), 79 (45), 71 (58), 55 (11). HRMS (ESI): calcd. for C9H17O5PNa H), 1.96–1.44 (m, 6 H) ppm. 13C NMR (100 MHz, CDCl3): δ =
[M + Na]+ 259.0706; found 259.0702.
200.8 (s), 74.3 (d), 68.7 (t), 53.2 (q, JC,P = 6.4 Hz, 2 C), 50.8 (t),
2
1
42.0 (t, JC,P = 127.8 Hz), 31.9 (t), 25.7 (t), 23.5 (t) ppm. MS (EI):
Dimethyl
[2-Oxo-3-(5-phenyltetrahydrofuran-2-yl)propyl]phos-
m/z (%) = 250 (1) [M]+·, 166 (18), 151 (83), 140 (88), 135 (10), 125
(49), 124 (100), 119 (17), 111 (14), 109 (75), 99 (21), 98 (11), 95
(10), 94 (66), 85 (26), 79 (43), 67 (18), 57 (18), 55 (26). HRMS
(ESI): calcd. for C10H19O5NaP [M + Na]+ 273.0862; found
273.0864.
phonate (6b): According to method B, alcohol 4b (32 mg, 0.2 mmol,
3 equiv.), phosphonate 1 (117 mg, 0.6 mmol, 3 equiv.), and [Ru]-III
(2ϫ6 mg, 2ϫ5 mol-%) led to 6b (63 mg, 0.2 mmol) after purifica-
tion on silica gel (AcOEt) followed by MPLC (AcOEt/MeOH =
99:1) as a brown oil. Yield: quant. as a mixture of 2 diastereomers
in a 60:40 ratio. IR: ν = 2957, 1714, 1453, 1255, 1026 cm–1. 1H
Dimethyl [2-Oxo-3-(6-phenyltetrahydro-2H-pyran-2-yl)propyl]phos-
phonate (6e): According to method B, alcohol 4e (35 mg, 0.2 mmol,
3 equiv.), phosphonate 1 (117 mg, 0.6 mmol, 3 equiv.), and [Ru]-III
(2ϫ6 mg, 2ϫ5 mol-%) led to 6e (59 mg, 0.18 mmol) after purifica-
˜
NMR (400 MHz, CDCl3, major diastereomer): δ = 7.34–7.21 (m,
3
3
5 H), 4.87 (tapp, J = 7.4 Hz, 1 H), 4.43 (m, 1 H), 3.78 (d, JH,P
=
3
11.2 Hz, 3 H), 3.77 (d, JH,P = 10.8 Hz, 3 H), 3.29–3.15 (m, 2 H),
3.08 (ddsystAB
,
2J = 16.2, 7.0 Hz, 1 H), 2.88 (ddsystAB
,
2J = 16.2, tion on silica gel (AcOEt/EP = 98:2) as a brown oil. Yield: 90%.
5.8 Hz, 1 H), 1.93–1.78 (m, 2 H), 1.75–1.63 (m, 2 H) ppm. 13C IR: ν = 2935, 2854, 1714, 1453, 1256, 1187, 1024 cm–1. H NMR
1
˜
2
NMR (100 MHz, CDCl3, major diastereomer): δ = 200.3 (s, JC,P (400 MHz, CDCl3): δ = 7.32–7.21 (m, 5 H), 4.38 (dd, J = 11.2,
3
= 6.3 Hz), 142.8 (s), 128.3 (d, 2 C), 127.3 (d), 125.8 (d, 2 C), 81.2
2.4 Hz, 1 H), 4.00 (m, 1 H), 3.75 (d, JH,P = 11.2 Hz, 3 H), 3.74
2
1
3
2
(d), 75.4 (d), 53.0 (q, JC,P = 6.0 Hz, 2 C), 50.1 (t), 42.0 (t, JC,P
=
(d, JH,P = 11.2 Hz, 3 H), 3.17 (dq, JH,P = 22.6 Hz, J = 13.8 Hz,
806
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© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2012, 801–809

Easy Access to Functionalized Heterocycles
2 H), 2.93 (dd, 2J = 15.6 Hz, 3J = 8.0 Hz, 1 H), 2.72 (dd, 2J =
15.6 Hz, 3J = 5.1 Hz, 1 H), 1.93 (m, 1 H), 1.83 (m, 1 H), 1.78–1.65
(m, 2 H), 1.48 (m, 1 H), 1.35 (m, 1 H) ppm. 13C NMR (100 MHz,
and [Ru]-III (2ϫ6 mg, 2ϫ5 mol-%) led to 8e (58 mg, 0.14 mmol)
after purification on silica gel (AcOEt) followed by MPLC (AcOEt/
MeOH = 99:1) as a brown oil. Yield: 72%. IR: ν = 3163, 2953,
˜
2
CDCl3): δ = 200.8 (s, JC,P = 6.3 Hz), 143.0 (s), 128.2 (d, 2 C),
2858, 1691, 1664, 1624, 1451, 1325, 1246, 1155, 1026 cm–1. 1H
2
127.2 (d), 125.8 (d, 2 C), 79.9 (d), 74.7 (d), 53.0 (q, JC,P = 6.2 Hz,
NMR (400 MHz, CDCl3): δ = 7.75 (d, J = 8.2 Hz, 2 H), 7.30 (d,
J = 8.8 Hz, 2 H), 6.89 (dt, J = 16.0, 7.2 Hz, 1 H), 6.19 (dtapp, J =
1
2 C), 50.6 (t), 42.2 (t, JC,P = 127.8 Hz), 33.2 (t), 31.0 (t), 23.7 (t)
3
ppm. MS (EI): m/z (%) = 308 (11), 221 (18), 193 (12), 179 (11), 166
(22), 151 (99), 124 (100), 117 (24), 104 (57), 94 (45), 79 (53), 65
(11), 55 (15). HRMS (ESI): calcd. for C16H23O5PNa [M + Na]+
349.1181; found 349.1173.
15.6, 1.3 Hz, 1 H), 5.42 (br. t, J = 6.0 Hz, 1 H), 3.78 (d, JH,P
=
11.2 Hz, 6 H), 3.23 (d, 2JH,P = 22.8 Hz, 2 H), 2.91 (qapp, J = 6.3 Hz,
2 H), 2.43 (s, 3 H), 2.23 (m, 2 H), 1.53–1.50 (m, 4 H) ppm. 13C
3
NMR (100 MHz, CDCl3): δ = 191.2 (s, JC,P = 5.9 Hz), 150.3 (d),
143.4 (s), 137.2 (s), 130.5 (d), 129.8 (d, 2 C) 127.2 (d, 2 C), 53.3 (q,
Dimethyl [2-Oxo-3-(6-pentyltetrahydro-2H-pyran-2-yl)propy]phos-
phonate (6f): According to method B, alcohol 4f (34 mg, 0.2 mmol,
3 equiv.), phosphonate 1 (117 mg, 0.6 mmol, 3 equiv.), and [Ru]-III
(2ϫ6 mg, 2ϫ5 mol-%) led to 6f (51 mg, 0.16 mmol) after purifica-
1
2JC,P = 6.8 Hz, 2 C), 42.9 (t), 39.1 (t, JC,P = 128.6 Hz), 31.9 (t),
28.7 (t), 24.7 (t), 21.7 (q) ppm. HRMS (ESI): calcd. for
C17H26NO6PSNa [M + Na]+ 426.1111; found 426.1101.
tion on silica gel (AcOEt/EP = 98:2) as a brown oil. Yield: 80%. Dimethyl [(E)-9-Methyl-8-(4-methylphenylsulfonamido)-2-oxodec-3-
IR: ν = 2931, 2858, 1716, 1458, 1375, 1346, 1258, 1197, 1029 cm–1.
en-1-yl]phosphonate (8f): According to method B, amine 7f (59 mg,
0.2 mmol, 3 equiv.), phosphonate 1 (117 mg, 0.6 mmol, 3 equiv.),
and [Ru]-III (2ϫ6 mg, 2ϫ5 mol-%) led to 8f (71 mg, 0.16 mmol)
˜
3
1H NMR (400 MHz, CDCl3): δ = 3.75 (d, JH,P = 11.2 Hz, 3 H),
3
3.74 (d, JH,P = 11.2 Hz, 3 H), 3.71 (m, 1 H), 3.25–3.06 (m, 3 H),
2.76 (ddsystAB, J = 15.2, 8.4 Hz, 1 H), 2.57 (ddsystAB, J = 15.2, after purification on silica gel (AcOEt) as a brown oil. Yield: 80%.
4.4 Hz, 1 H), 1.81–1.73 (m, 1 H), 1.58–1.04 (m, 13 H), 0.83 (t, J =
IR: ν = 3174, 2957, 2873, 1718, 1691, 1664, 1624, 1598, 1455, 1246,
˜
1
7.0 Hz, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 201.2 (s, 2JC,P 1156, 1026 cm–1. H NMR (400 MHz, CDCl3): δ = 7.75 (br. d, J
2
= 6.0 Hz), 78.2 (d), 74.5 (d), 53.1 (q, JC,P = 6.7 Hz, 2 C), 50.7 (t),
= 8.0 Hz, 2 H), 7.28 (d, J = 8.0 Hz, 2 H), 6.83 (dt, J = 16.0, 6.8 Hz,
1 H), 6.16 (dt, J = 16.0, 1.4 Hz, 1 H), 5.17 (d, J = 8.8 Hz, 1 H),
3.80 (d, 3JH,P = 11.2 Hz, 3 H), 3.77 (d, 3JH,P = 11.2 Hz, 3 H), 3.38–
3.06 (m, 3 H), 2.42 (s, 3 H), 2.24–2.04 (m, 2 H), 1.67 (m, 1 H),
1
42.2 (t, JC,P = 128.3 Hz), 36.5 (t), 32.0 (t), 31.6 (t), 31.4 (t), 25.4
(t), 23.6 (t), 22.8 (t), 14.2 (q) ppm. MS (EI): m/z (%) = 302 (5), 221
(14), 210 (14), 208 (18), 193 (11), 167 (41), 166 (24), 151 (100), 135
(17), 124 (54), 119 (11), 111 (13), 109 (54), 100 (24), 95 (19), 94
1.49–1.23 (m, 4 H), 0.76 (t, J = 6.8 Hz, 6 H) ppm. 13C NMR
2
(26), 93 (11), 81 (15), 79 (25), 69 (10), 57 (10), 54 (10). HRMS (100 MHz, CDCl3): δ = 191.2 (s, JC,P = 6.3 Hz), 150.6 (d), 143.1
(ESI): calcd. for C15H29O5NaP [M + Na]+ 343.1641; found
343.1645.
(s), 139.1 (s), 130.4 (d), 129.6 (d, 2 C), 127.0 (d, 2 C), 59.3 (d), 53.3
2
1
(q, JC,P = 6.3 Hz, 2 C), 39.2 (t, JC,P = 128.5 Hz), 32.2 (t), 31.9
(d), 30.6 (t), 24.1 (t), 21.6 (q), 18.1 (q, 2 C) ppm. HRMS (ESI):
calcd. for C20H32NO6PSNa [M + Na]+ 468.1580; found 468.1572.
tert-Butyl Dec-1-en-5-ylcarbamate (7b): 2,2,6,6-Tetramethyl-1-pip-
eridinyloxyl (TEMPO; 30 mg, 0.2 mmol, 0.2 equiv.) and [bis(ace-
toxy)iodo]benzene (BAIB; 370 mg, 1.15 mmol, 1.15 equiv.) were
added to a stirred solution of alcohol 4c (155 mg, 1 mmol, 1 equiv.)
in CH2Cl2 (4 mL), and the mixture was stirred at room temperature
until complete conversion of alcohol was observed, as monitored
by TLC and GC–MS. After 20 h, NaBH3CN (414 mg, 2 mmol,
2 equiv.), methanol (2 mL), and ammonium formate (630 mg,
10 mmol, 5 equiv.) were added to the reaction mixture. After 20 h,
the mixture was quenched carefully with aq. NaOH (10 mol-%,
10 mL) and extracted with Et2O (3ϫ20 mL). The crude material
was then diluted in CH2Cl2 (2 mL) and Et3N (0.29 mL, 2 mmol,
2 equiv.) was added. The reaction was cooled to 0 °C and Boc2O
(240 mg, 1.1 mmol, 1.1 equiv.) was added. After 16 h at room tem-
perature, the reaction was diluted with CH2Cl2 (20 mL), and the
organic layer was washed with 10% HCl (10 mL) and NaHCO3
(10 mL). The organic layer was dried with MgSO4, filtered, and
evaporated to afford after purification on silica gel (EP/AcOEt =
98:2 to 90:10) 7b (144 mg, 0.56 mmol) as a colorless oil. Yield:
Dimethyl [(E)-8-(4-Methylphenylsulfonamido)-2-oxo-8-phenyloct-3-
en-1-yl]phosphonate (8g): According to method B, amine 7g (66 mg,
0.2 mmol, 3 equiv.), phosphonate 1 (117 mg, 0.6 mmol, 3 equiv.),
and [Ru]-III (2ϫ6 mg, 2ϫ5 mol-%) led to 8g (81 mg, 0.17 mmol)
after purification on silica gel (AcOEt) as a brown oil. Yield: 88%.
IR: ν = 3258, 2925, 2854, 1664, 1624, 1494, 1456, 1323, 1244, 1155,
˜
1026 cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.49 (br. d, J =
8.4 Hz, 2 H), 7.12–7.07 (m, 3 H), 7.05 (d, J = 8.4 Hz, 2 H), 7.03–
6.98 (m, 2 H), 6.86 (dt, J = 16.0, 6.8 Hz, 1 H), 6.17 (br. dt, J =
16.0, 1.4 Hz, 1 H), 6.04 (d, J = 8.4 Hz, 1 H), 4.25 (m, 1 H), 3.79
2
(d, 2JH,P = 11.6 Hz, 3 H), 3.76 (d, JH,P = 11.6 Hz, 3 H), 3.35–3.10
(m, 2 H), 2.32 (s, 3 H), 2.29–2.10 (m, 2 H), 1.85–1.38 (m, 4 H)
2
ppm. 13C NMR (100 MHz, CDCl3): δ = 191.0 (s, JC,P = 5.9 Hz),
150.2 (d), 142.6 (s), 141.2 (s), 138.1 (s), 130.5 (d), 129.1 (d, 2 C),
128.4 (d, 2 C), 127.2 (d), 126.9 (d, 2 C), 126.4 (d, 2 C), 58.2 (d),
2
1
53.2 (q, JC,P = 6.3 Hz, 2 C), 39.0 (t, JC,P = 128.8 Hz), 36.7 (t),
31.7 (t), 24.1 (t), 21.4 (q) ppm. HRMS (ESI): calcd. for
C23H30NO6PSNa [M + Na]+ 502.1424; found 502.1407.
56%. IR: ν = 3338, 2930, 2858, 1685, 1522, 1453, 1390, 1365, 1246,
˜
1
1171 cm–1. H NMR (400 MHz, CDCl3): δ = 5.78 (ddt, J = 17.1,
tert-Butyl
2-[3-(Dimethoxyphosphoryl)-2-oxopropyl]-5-phenylpyr-
10.2, 6.7 Hz, 1 H), 5.02–4.88 (m, 2 H), 4.13 (br. d, J = 8.4 Hz, 1
H), 3.53 (m, 1 H), 2.13–1.97 (m, 2 H), 1.57–1.44 (m, 2 H), 1.45–
1.35 (m, 11 H), 1.33–1.17 (m, 6 H), 0.84 (br. t, J = 6.8 Hz, 3 H)
ppm. 13C NMR (100 MHz, CDCl3): δ = 155.8 (s), 138.5 (d), 114.8
(t), 79.0 (s), 50.5 (d), 35.7 (t), 35.0 (t), 31.9 (t), 30.4 (t), 28.6 (q, 3
C), 25.7 (t), 22.8 (t), 14.2 (q) ppm. MS (EI): m/z (%) = 201 (1), 144
(22), 128 (26), 100 (36), 84 (42), 67 (13), 59 (10), 57 (100), 55 (14).
HRMS (ESI): calcd. for C15H29NO2 [M + Na]+ 278.2090; found
278.2097.
rolidine-1-carboxylate (9a): According to method B, amine 7a
(52 mg, 0.2 mmol, 3 equiv.), phosphonate 1 (117 mg, 0.6 mmol,
3 equiv.), and [Ru]-III (2ϫ6 mg, 2ϫ5 mol-%) led to 9a (53 mg,
0.13 mmol) after purification on silica gel (AcOEt) followed by
MPLC (AcOEt/MeOH = 99:1) as a brown oil. Yield: 65% as a
mixture of two diastereomers in a 70:30 ratio. IR: ν = 2972, 1707,
˜
1683, 1452, 1393, 1375, 1258, 1169, 1036 cm–1. 1H NMR
(400 MHz, CDCl3, mixture of diastereomers = 70:30): δ = 7.32–
7.18 (m, 3 H), 7.11–7.07 (m, 2 H), 4.98 (br. d, J = 8.0 Hz, 0.3 H),
3
Dimethyl [(E)-8-(4-Methylphenylsulfonamido)-2-oxooct-3-en-1-yl]-
phosphonate (8e): According to method B, amine 7e (51 mg,
0.2 mmol, 3 equiv.), phosphonate 1 (117 mg, 0.6 mmol, 3 equiv.),
4.83 (br. d, J = 8.0 Hz, 0.7 H), 4.59–4.45 (m, 1 H), 3.80 (2 d, J =
11.2 Hz, 6 H), 3.32–3.02 (m, 3 H), 2.80 (ddsystAB, J = 16.8, 9.2 Hz,
1 H), 2.33 (m, 1 H), 2.20 (m,1 H), 1.74 (m, 1 H), 1.62 (m, 1 H),
Eur. J. Org. Chem. 2012, 801–809
© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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807

T. Cochet, D. Roche, V. Bellosta, J. Cossy
FULL PAPER
1.61, 1.43, 1.12 (3s, 9 H) ppm. 13C NMR (100 MHz, CDCl3, major
3
8.4 Hz, 1 H), 4.14 (m, 1 H), 3.81 (d, JH,P = 11.2 Hz, 6 H), 3.77
2
diastereomer): δ = 200.5 (s, JC,P = 5.9 Hz), 153.9 (s), 144.9 (s),
(m, 1 H), 3.30–2.97 (m, 3 H), 2.44 (s, 3 H), 2.43–2.32 (m, 2 H),
1.80–1.71 (m, 2 H) ppm. HRMS (ESI): calcd. for C22H28NO6PSNa
[M + Na]+ 488.1267; found 488.1256.
128.1 (d, 2 C), 126.5 (d), 125.2 (d, 2 C), 79.5 (s), 61.7 (d), 54.1 (d),
2
1
53.1 (q, JC,P = 6.8 Hz, 2 C), 47.8 (t), 41.5 (t, JC,P = 126.6 Hz),
32.5 (t), 28.0 (s, 3 C), 27.6 (t) ppm. 13C NMR (100 MHz, CDCl3,
tert-Butyl
2-[(E)2-Oxo-4-phenylbut-3-en-1-yl]pyrrolidine-1-carb-
2
minor diastereomer): δ = 200.3 (s, JC,P = 6.9 Hz), 153.3 (s), 143.5
oxylate (10h): According to method B, amine 7h (37 mg, 0.2 mmol,
3 equiv.), phosphonate 1 (117 mg, 0.6 mmol, 3 equiv.), and [Ru]-
III (2ϫ6 mg, 2ϫ5 mol-%) led to, after purification on silica gel
(AcOEt), 9h as an inseparable mixture with phosphonate 1. The
mixture was then dissolved in MeCN (5 mL), K2CO3 (221 mg,
0.8 mmol, 2 equiv.) was added, and the mixture was stirred at room
temperature. After 30 min, benzaldehyde (85 mg, 0.8 mmol,
2 equiv.) was added, and the mixture was heated at reflux for 16 h.
(s), 128.4 (d, 2 C), 126.3 (d), 125.0 (d, 2 C), 80.0 (s), 61.0 (d), 53.6
(d), 52.9 (q, 2JC,P = 6.8 Hz, 2 C), 48.4 (t), 41.5 (t, 1JC,P = 126.6 Hz),
31.7 (t), 28.4 (s, 3 C), 28.0 (t) ppm. HRMS (ESI): calcd. for
C20H30NO6PNa [M + Na]+ 434.1703; found 434.1704.
tert-Butyl 2-[3-(Dimethoxyphosphoryl)-2-oxopropyl]-5-pentylpyrrol-
idine-1-carboxylate (9b): According to method B, amine 7b (51 mg,
0.2 mmol, 3 equiv.), phosphonate 1 (117 mg, 0.6 mmol, 3 equiv.),
and [Ru]-III (2ϫ6 mg, 2ϫ5 mol-%) led to 9b (34 mg, 0.09 mmol) The volatiles were removed under reduced pressure, and the crude
after purification on silica gel (AcOEt) followed by MPLC (AcOEt/
MeOH = 99:1) as a brown oil. Yield: 43% as a mixture of two
material was dissolved in AcOEt (10 mL). The organic layer was
washed with water (5 mL) and brine (5 mL), and the organic layers
phases were combined, dried with MgSO4, filtered, and evaporated
diastereomers in a 70:30 ratio. IR: ν = 2957, 2928, 2857, 1713,
˜
1684, 1456, 1391, 1367, 1254, 1171, 1110, 1025 cm–1. 1H NMR to afford after purification on silica gel (EP/AcOEt = 95:5 to 80:20)
(400 MHz, CDCl3, mixture of diastereomers = 70:30): δ = 4.24– enone 10h (50 mg, 16 mmol) as a slightly yellow oil. Yield: 80%
4.25 (m, 1 H), 3.79 (d, 3JH,P = 11.0 Hz, 6 H), 3.73 (m, 0.3 H), 3.64
(m, 0.7 H), 3.25–3.02 (m, 3 H), 2.66–2.59 (m, 1 H), 2.12–2.01 (m,
1 H), 1.91–1.80 (m, 1 H), 1.68–1.55 (m, 3 H), 1.45 (s, 9 H), 1.36–
(over two steps). IR: ν = 2973, 2877, 1686, 1610, 1450, 1394, 1366,
˜
1
1167, 1115 cm–1. H NMR (400 MHz, CDCl3, equimolar ratio of
two rotamers): δ = 7.72–7.52 (m, 3 H), 7.40 (br. s, 3 H), 6.73 (d, J
1.18 (m, 7 H), 0.90–0.86 (m, 3 H) ppm. 13C NMR (100 MHz, = 16.0 Hz, 1 H), 4.26 (m, 1 H), 3.48–3.12 (m, 3 H), 2.63 (m, 1 H),
CDCl3, major diastereomer): δ = 200.6 (s), 153.8 (s), 79.3 (s), 57.8
2.05 (s, 1 H), 1.86 (m, 2 H), 1.75 (m, 1 H), 1.48 (s, 9 H) ppm. 13C
(d), 53.1 (q, 2JC,P = 6.9 Hz, 2 C), 47.5 (d), 41.5 (t, 1JC,P = 127.4 Hz),
NMR (100 MHz, CDCl3, equimolar ratio of two rotamers): δ =
33.8 (t), 31.7 (t), 28.5 (q, 3 C), 28.7 (t), 28.1 (t), 27.3 (t), 26.3 (t), 199.3, 198.7 (s), 154.4, 154.3 (d), 143.3, 142.9 (d), 134.6, 134.4 (s),
22.6 (t), 14.0 (q) ppm. HRMS (ESI): calcd. for C19H36NO6PNa [M
130.6, 130.4 (d), 129.0–126.5 (d, 5 C), 79.6, 79.2 (s), 54.3, 54.0 (d),
46.7, 46.2, 45.9, 44.9 (t, 2 C), 31.4, 30.4 (t), 28.6 (q, 3 C), 23.6, 22.9
(t) ppm. MS (EI): m/z (%) = 260 (3), 214 (10), 131 (51), 110 (10),
103 (30), 83 (24), 77 (22), 70 (44), 69 (11), 68 (16), 57 (100), 56
(13). HRMS (ESI): calcd. for C19H25NO3Na [M + Na]+ 338.1727;
found 338.1724.
+ Na]+ 428.2172; found 428.2175.
Dimethyl [2-Oxo-3-(1-tosylpyrrolidin-2-yl)propy]phosphonate (9c):
According to method B, amine 7c (48 mg, 0.2 mmol, 3 equiv.),
phosphonate
1 (117 mg, 0.6 mmol, 3 equiv.), and [Ru]-III
(2ϫ6 mg, 2ϫ5 mol-%) led to 9c (43 mg, 0.11 mmol) after purifica-
tion on silica gel (AcOEt) followed by MPLC (AcOEt/MeOH =
tert-Butyl
(10i): According to method B, amine 7i (40 mg, 0.2 mmol, 3 equiv.),
1402, 1374, 1253, 1198, 1157, 1023 cm–1. 1H NMR (400 MHz, phosphonate
(117 mg, 0.6 mmol, 3 equiv.), and [Ru]-III
[(5E,8E)-7-Oxo-9-phenylnona-5,8-dien-1-yl]carbamate
99:1) as a brown oil. Yield: 55%. IR: ν = 2957, 1713, 1598, 1451,
˜
1
CDCl3): δ = 7.71 (br. d, J = 8.2 Hz, 2 H), 7.33 (d, J = 7.9 Hz, 2
H), 3.96 (m, 1 H), 3.80 (d, JH,P = 11.3 Hz, 6 H), 3.44 (m, 1 H),
(2ϫ6 mg, 2ϫ5 mol-%) led to, after purification on silica gel (Ac-
OEt), 9i as an inseparable mixture with phosphonate 1. The mix-
3
3.30 (ddsystAB, J = 18.1, 3.8 Hz, 1 H), 3.26–3.03 (m, 3 H), 2.94 ture was then dissolved in MeCN (3 mL), K2CO3 (221 mg,
(ddsystAB, J = 18.1, 9.2 Hz, 1 H), 2.44 (s, 3 H), 1.84–1.71 (m, 2 H),
0.8 mmol, 2 equiv.) was added, and the mixture was stirred at room
temperature. After 30 min, benzaldehyde (85 mg, 0.8 mmol,
2 equiv.) was added, and the mixture was heated at reflux for 16 h.
1.61–1.43 (m, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 200.5
2
(s, JC,P = 6.3 Hz), 143.8 (s), 134.0 (s), 129.9 (d, 2 C), 127.7 (d, 2
2
2
C), 55.9 (d), 53.3 (q, JC,P = 6.4 Hz), 53.1 (q, JC,P = 6.4 Hz), 51.1 The volatiles were removed under reduced pressure, and the crude
1
(t), 49.3 (t), 42.4 (t, JC,P = 126.7 Hz), 32.1 (t), 24.0 (t), 21.7 (q)
ppm. HRMS (ESI): calcd. for C16H24NO6PSNa [M + Na]+
412.0954; found 412.0939.
material was dissolved in AcOEt (10 mL). The organic layer was
washed with water (5 mL) and brine (5 mL), dried with MgSO4,
filtered, and evaporated to afford, after purification on silica gel
(EP/AcOEt = 95:5 to 80:20), enone 10i (46 mg, 14 mmol) as a
Dimethyl
[2-Oxo-3-(5-phenyl-1-tosylpyrrolidin-2-yl)propyl]phos-
slightly yellow oil. Yield: 73% (over two steps). IR: ν = 3353, 2975,
˜
phonate (9d): According to method B, amine 7d (63 mg, 0.2 mmol,
3 equiv.), phosphonate 1 (117 mg, 0.6 mmol, 3 equiv.), and [Ru]-III
(2ϫ6 mg, 2ϫ5 mol-%) led to 9d (43 mg, 0.12 mmol) after purifica-
tion on silica gel (AcOEt) followed by MPLC (AcOEt/MeOH =
99:1) as a brown oil. Yield: 60% as a mixture of diastereomers in
2931, 2863, 1694, 1660, 1629, 1600, 1517, 1450, 1365, 1275, 1251,
1170 cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.65 (d, J = 16.0 Hz,
1 H), 7.60–7.56 (m, 2 H), 7.42–7.37 (m, 3 H), 7.02–6.94 (m, 2 H),
6.45 (dt, J = 15.6, 1.6 Hz, 1 H), 4.53 (br. s, 1 H), 3.15 (br. m, 2 H),
2.31 (m, 2 H), 1.57–1.52 (m, 4 H), 1.45 (s, 9 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 189.2 (s), 156.0 (s), 147.5 (d), 143.1 (d),
134.8 (s), 130.4 (d), 129.5 (d), 128.9 (d, 2 C), 128.3 (d, 2 C), 124.9
(d), 79.2 (s), 40.3 (t), 32.3 (t), 29.7 (t), 28.4 (q, 3 C), 25.4 (t) ppm.
HRMS (ESI): calcd. for C20H27NO3Na [M + Na]+ 352.1883; found
352.1885.
a 80:20 ratio. IR: ν = 2956, 2853, 1712, 1598, 1495, 1454, 1337,
˜
1258, 1155, 1028 cm–1. 1H NMR (400 MHz, CDCl3, major dia-
stereomer): δ = 7.20–6.80 (m, 9 H), 5.01 (d, J = 8.4 Hz, 1 H), 4.54
3
(m, 1 H), 3.82 (d, JH,P = 11.2 Hz, 6 H), 3.66 (m, 1 H), 3.30–2.97
(m, 3 H), 2.43–2.32 (m, 2 H), 2.33 (s, 3 H), 1.80–1.71 (m, 2 H)
ppm. 13C NMR (100 MHz, CDCl3, major diastereomer): δ = 200.6
2
(s, JC,P = 6.3 Hz), 142.7 (s), 141.4 (s), 138.0 (s), 129.1 (d, 2 C),
tert-Butyl
2-[(E)-2-Hydroxy-4-phenylbut-3-en-1-yl]pyrrolidine-1-
128.3 (d, 2 C), 127.2 (d), 127.1 (d, 4 C), 64.2 (d), 56.5 (d), 53.4 (q,
carboxylate (11): To a solution of 9h (57 mg, 0.18 mmol, 1 equiv.)
in THF (5 mL) at 0 °C was added LiAlH(OtBu)3 (1 m in THF,
186 μL, 0.186 mmol, 1.03 equiv.). After 3 h at 0 °C, the reaction
2
1
2JC,P = 6.3 Hz), 53.2 (q, JC,P = 6.3 Hz), 50.3 (t), 42.1 (t, JC,P
=
127.5 Hz), 32.9 (t), 30.6 (t), 21.6 (q) ppm. 1H NMR (400 MHz,
CDCl3, minor diastereomer): δ = 7.40–6.91 (m, 9 H), 4.65 (d, J = was quenched by addition of a few drops of cold water and AcOEt
808
www.eurjoc.org
© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2012, 801–809

Easy Access to Functionalized Heterocycles
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and stirred for 1 h. The mixture was filtered through Celite to af-
ford 11 (44 mg, 0.14 mmol) as a slightly yellow oil. Yield: 81%. IR:
1
ν = 3670, 3408, 2973, 1670, 1405, 1250, 1168, 1111, 1067 cm–1. H
˜
NMR (400 MHz, CDCl3): δ = 7.40–7.15 (m, 5 H), 6.60 (d, J =
16.1 Hz, 1 H), 6.24 (dd, J = 16.0, 5.6 Hz, 1 H), 4.40 (br. s, 1 H),
4.10 (br. s, 1 H), 3.31 (m, 2 H), 2.03–1.84 (m, 4 H), 1.71–1.50 (m,
2 H), 1.48–1.43 (m, 9 H) ppm. 13C NMR (100 MHz, CDCl3): δ =
155.6 (s), 137.2 (s), 133.0 (d), 128.8 (d), 128.5 (d, 2 C), 127.3 (d),
126.4 (d, 2 C), 79.9 (s), 70.7 (d), 55.0 (d), 46.4 (t), 43.6 (t), 32.1 (t),
28.5 (q, 3 C), 23.8 (t) ppm. MS (EI): m/z (%) = 243 (1), 129 (11),
115 (14), 114 (44), 91 (14), 85 (18), 70 (100), 57 (87), 56 (20), 55
(15). HRMS (ESI): calcd. for C19H27NO3Na [M + Na]+ 340.1883;
found 340.1884.
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Received: September 24, 2011
Published Online: December 5, 2011
Eur. J. Org. Chem. 2012, 801–809
© 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
809