[2,3]-Sigmatropic rearrangement of ynamides: Preparation of α-amino allenephosphonates

Article abstract of DOI:10.1021/jo300790m

α-Amino allenephosphonates were easily prepared in two steps from protected amines, propargyl alcohols, and chlorophosphites. First, ynamides were synthesized from unprotected 1-bromopropargyl alcohols using a copper(II) catalyzed coupling reaction. In the second step, the previously prepared ynamides were transformed directly to allenes through a [2,3]-sigmatropic rearrangement of propargyl phosphites. This efficient method led to the formation of a series of α-amino allenephosphonates with diverse substituents on the amine, the phosphonate, and the allene moieties.

Full text of DOI:10.1021/jo300790m

Note
pubs.acs.org/joc
[2,3]-Sigmatropic Rearrangement of Ynamides: Preparation of
α‑Amino Allenephosphonates
Filipe Gomes, Antoine Fadel, and Nicolas Rabasso*
̀ ́ ̂ ́
Laboratoire de Synthese Organique et Methodologie, ICMMO, UMR CNRS 8182, Bat. 420, Universite Paris-Sud, 15 rue Georges
Clemenceau, 91405 Orsay Cedex, France
S
* Supporting Information
ABSTRACT: α-Amino allenephosphonates were easily pre-
pared in two steps from protected amines, propargyl alcohols,
and chlorophosphites. First, ynamides were synthesized from
unprotected 1-bromopropargyl alcohols using a copper(II)
catalyzed coupling reaction. In the second step, the previously
prepared ynamides were transformed directly to allenes
through a [2,3]-sigmatropic rearrangement of propargyl
phosphites. This efficient method led to the formation of a series of α-amino allenephosphonates with diverse substituents
on the amine, the phosphonate, and the allene moieties.
ver the past few years, ynamides have received
considerable attention due to their ease of preparation
Scheme 1. Three-Step Sequence for the Preparation of
Amino Allenephosphonates
O
by copper catalysis.1,2 Ynamides appeared to be useful synthons
in natural product synthesis. Indeed, in 2005 Hsung and co-
workers reported the synthesis of desbromoarborescidines A
and C based on an arene−ynamide cyclization step.3
Recently we reported the highly regio- and stereoselective
synthesis of β-amino vinylphosphonates by hydrophosphony-
lation of ynamides.4 Continuing our efforts toward the
preparation of amino vinylphosphonates, we became interested
in amino allenephosphonates. Although the synthesis and
transformation of allenephosphonates5 and alleneamides6,7
have been well described in the literature, to date the synthesis
of amino allenephosphonates has not been reported. In
addition to their obvious use as precursors of α-amino-
phosphonates,8 α-amino allenephosphonates represent an
interesting synthon due to the allene moiety that can be later
functionalized to produce bioactive unsaturated aminophosph-
onates.9,10 Herein we report a straightforward synthesis of α-
amino allenephosphonates by using ynamides as starting
material.
was performed in THF. However, in that case the temperature
was crucial; at 0 °C multiple products were obtained, whereas a
clean amino allenephosphonate 5c was obtained when the
reaction was run at −78 °C and slowly warmed to rt.
The synthesis starts with the copper(II) coupling reaction
between amines 1 and 1-bromoalkyne 2 to furnish ynamides 3,
following the protocol reported by Hsung and co-workers.11
Deprotection of TBS ethers 3 led to the alcohols 4, which were
treated with diethyl chlorophosphite in the presence of
triethylamine to give the corresponding α-amino allenephosph-
onates 5 in good yields (Scheme 1).12−16 Although efficient for
the formation of α-amino allenephosphonates from tosylamine
1a and oxazolidinone 1b, this sequence failed with
pyrrolidinone 1c. Indeed, in that case, the yield for the
preparation of ynamide 3c was never higher than 3%.
Improvements were made by using alkynylcopper reagents, as
recently reported by Evano and co-workers,17 which led to
ynamide 3c in 41% yield. Moreover, because of the low
solubility of ynamide 4c in Et2O, the synthesis of the allene 5c
Although efficient for the preparation of α-amino allene-
phosphonates as 5, this three-step sequence suffers from the use
of TBS protected propargyl alcohol 2. In order to shorten this
synthesis and avoid the protection of 2 as a silyl ether, N-tosyl
ynamides 4a and 7 were prepared directly from unprotected 1-
bromopropargyl alcohols 6 and N-tosyl benzylamine 1a. Thus,
the resulting ynamides 4a and 7, prepared in moderate to
excellent yields, were subjected to a [2,3]-sigmatropic
rearrangement, by addition of diethyl chlorophosphite in the
presence of triethylamine, to form the α-amino allenephosph-
onates 8 in good yields (Table 1). Although efficient for the
Received: April 20, 2012
© XXXX American Chemical Society
A
dx.doi.org/10.1021/jo300790m | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Note
Table 1. Scope and Limitations: Bromoalkyne Variation
Scheme 2. Scope and Limitations: Phosphite Variation
ynamide 7c by 4a, which does not bear the gem-dimethyl group,
only moderately improves the yield of the [2,3]-sigmatropic
rearrangement to 33% (Scheme 3).
Scheme 3. Effect of the Steric Hindrance on the Nitrogen
Atom
To extend the scope of this [2,3]-sigmatropic rearrangement
of ynamides, the same strategy was efficiently applied to the
formation of α-amino allenephosphine oxide 11 with diphenyl
chlorophosphine reagent (Scheme 4).
Scheme 4. Preparation of α-Amino Allenephosphine Oxide
11
preparation of α-amino allenephosphonates 8f and 8g, this
strategy was challenging for the synthesis of precursor ynamides
7f and 7g. Indeed, for those the benzyl alcohol moiety is
unstable, and decomposition occurred during the purification,
which led to the ynamides 7f and 7g in moderate to low yields,
50 and 24%, respectively.
Next, we investigated the effect of the chlorophosphite
reagent on the formation of the amino allenephosphonates
(Scheme 2). Cyclic18 and acyclic19 chlorophosphite reagents
were used to prepare allenephosphonates 9.
The low yields observed in the case of allenephosphonates 9
are explained by the steric hindrance of both the
chlorophosphite reagent and the protecting group on the
nitrogen atom. Indeed, further studies show that replacement of
the tosyl group in ynamide 7c by the mesyl group 10 increased
the yield of allenephosphonate 9e to 79%. Replacement of
Finally, we investigated the influence of the electron-
withdrawing groups on the nitrogen atom (Table 2). When
the amine moiety is protected by a sulfonate and a benzyl
group, the corresponding ynamides 10, 12a and α-amino
allenephosphonates 13a,b were obtained in good yields.
However, with aniline derivatives, formation of ynamide 12c
required some adjustments. Indeed, our protocol without the
use of protecting groups on the 1-bromopropargyl alcohol
failed to provide the ynamide 12c in the previous conditions.
The use of the protocol developed by Stahl and co-workers
provided the ynamide 12c in moderate yield (40%).20 Next, the
latter was subjected to a [2,3]-rearrangement with diethyl
chlorophosphite to furnish α-amino allenephosphonate 13c in a
moderate 53% yield. These conditions are difficult to adapt to
all types of amines. Indeed, oxazolidinone 1b was converted to
ynamide 12d in a low 21% yield. Moreover, the conversion to
B
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Note
of standard procedures. Reagent grade solvents were used without
purification for all extractions and workup procedures. Rf values refer
to values obtained by TLC on 0.25 mm silica gel plates (60-F254).
Flash chromatography was performed on silica gel 60 (15−40 μm)
using a CombiFlash apparatus with various mixtures of ethyl acetate
(EtOAc) and petroleum ether (PE). Yields refer to chromato-
graphically and spectroscopically pure compounds. NMR measure-
ments were performed at either 250, 300, or 360 MHz. HRMS spectra
were recorded on a MicroTOFq spectrometer. 1-Bromopropargyl
alcohols 2 and 6 were prepared following the protocol reported in the
literature.21
Table 2. Scope and Limitations: α-Amino
Allenephosphonates Formation with Representative
Ynamides
General Method for the Preparation of Ynamides (Proce-
dure A). Amines (2.19 mmol), CuSO4·5H2O (0.22 mmol), 1,10-
phenanthroline (0.44 mmol), and K3PO4 (4.37 mmol) were heated to
70 °C in 5 mL of dry toluene under inert atmosphere. Bromoalkyne
(3.28 mmol) in 5 mL of dry toluene was then slowly added. After 2−
12 h at 70 °C, the mixture was cooled to room temperature, filtered
through a pad of Celite, and concentrated in vacuo. Purification by
flash chromatography on silica gel yielded the ynamides.
General Procedure for the Preparation of α-Amino
Allenephosphonates (Procedure B). To a solution of ynamide
(1.77 mmol) in 10 mL of anhydrous diethyl ether cooled at 0 °C were
added triethylamine (1.94 mmol) and chlorophosphite (1.94 mmol).
After 1−18 h of stirring at room temperature, the mixture was filtered
through a pad of Celite, the solvent was removed in vacuo, and crude
product was purified by flash chromatography on silica gel to yield the
amino allenephosphonates.
N-Benzyl-N-[3-(tert-butyldimethylsilyloxy)prop-1-ynyl]-4-
methylbenzenesulfonamide (3a). Prepared according to proce-
dure A (3.3 g, 84% yield). Analytical data matched with that reported
in the literature.22
3-[3-(tert-Butyldimethylsilyloxy)prop-1-ynyl]oxazolidin-2-
one (3b).23 Prepared according to procedure A (428 mg, 51% yield).
Analytical data matched with that reported in the literature.23
1-[3-(tert-Butyldimethylsilyloxy)prop-1-ynyl]pyrrolidin-2-
one (3c). Yanmide 3c was prepared according to the procedure
reported by Evano and co-workers.17 To a mixture of pyrrolidinone 1c
(24.6 mmol) and alkynylcopper (6.15 mmol), 12 mL of dry
acetonitrile was added. Then, TMEDA (6.15 mmol) was added, and
the mixture was stirred at room temperature under oxygen. After 3
days of stirring, the dark green solution was filtered through a pad of
Celite, and the solvent was removed in vacuo, and then resulting crude
product was purified by flash chromatography on silica gel (EtOAc/PE
20/80 to 80/20) to lead to ynamide 3c, as a white solid (640 mg, 41%
yield): mp 60−62 °C; Rf = 0.29 (EtOAc/PE = 20/80); 1H NMR (250
MHz, CDCl3) δ 4.46 (s, 2H), 3.67 (t, J = 7.3 Hz, 2H), 2.41 (dd, J =
7.3, 8.5 Hz, 2H), 2.10 (quint, J = 7.6 Hz, 2H), 0.88 (s, 9H), 0.10 (s,
6H); 13C NMR (90.56 MHz, CDCl3) δ 176.2, 76.0, 71.5, 51.9, 49.9,
29.7, 25.9, 18.9, 18.9, −5.0; HRMS (ESI) m/z [MH+] calcd for
C13H24NO2Si 254.1571, found 254.1567.
a
Preparation of ynamide 12c was performed following the protocol
reported by Stahl and co-workers.20 BRSM: Based on recovered
starting material.
b
the corresponding allenephosphonate was also difficult (26%
yield, 40% based on recovered starting material). This result
can be explained by the steric hindrance induced by the
oxazolidinone moiety and the presence of the gem-dimethyl
group in the ynamide 12d.
Extension of this methodology to other electron-withdrawing
groups on the amine moiety such as Boc, acetyl, trifluoroacetyl,
pyrrolidinyl, and phosphoryl failed to provide the respective
ynamides by direct coupling with 1-bromopropargyl alcohol 6c.
In conclusion, a variety of ynamides were easily transformed
into α-amino allenephosphonates via a [2,3]-sigmatropic
rearrangement of propargyl phosphites. This strategy yielded
allenephosphonates in two steps from readily available amines
and unprotected propargyl alcohols. Further developments are
under way in our group to prepare these α-amino
allenephosphonates in an enantiomerically pure form and
investigate their reactivities.
N-Benzyl-N-(3-hydroxyprop-1-ynyl)-4-methylbenzenesulfo-
namide (4a).24 Deprotection of ynamide 4a followed the protocol
reported by Zhang and co-workers (224 mg, 57% yield).24 Direct
synthesis of ynamide 4a from amine 1a followed procedure A (355
mg, 59% yield).
3-(3-Hydroxyprop-1-ynyl)oxazolidin-2-one (4b).23 Deprotec-
tion of ynamide 3b followed the protocol reported by Chemla and co-
workers (150 mg, 67% yield).23
1-(3-Hydroxyprop-1-ynyl)pyrrolidin-2-one (4c). Flash chroma-
tography: EtOAc/PE 50/50 to 80/20; colorless oil, 255 mg, 69% yield;
Rf = 0.24 (EtOAc/PE = 80/20); 1H NMR (250 MHz, CDCl3) δ 4.18
(s, 2H), 4.09 (br s, 1H), 3.49 (s, 2H), 2.28−2.20 (m, 2H), 1.90 (quint,
J = 7.6 Hz, 2H); 13C NMR (62.9 MHz, CDCl3) δ 176.7, 75.6, 71.3,
50.0, 49.5, 29.2, 18.3; HRMS (ESI) m/z [MH+] calcd for C7H10NO2
140.0706, found 140.0705.
Diethyl 1-(N-Benzyl-4-methylphenylsulfonamido)propa-1,2-
dienylphosphonate (5a). Prepared according to procedure B. Flash
chromatography: EtOAc/PE 20/80 to 60/40; colorless oil, 110 mg,
77% yield; Rf = 0.53 (EtOAc/PE = 90/10); IR (neat) 3084, 3062,
2929, 2908, 1868, 2239, 1955, 1927, 1597, 1492, 1455 cm−1; 1H NMR
EXPERIMENTAL SECTION
■
General Methods. All reactions were carried out under argon with
magnetic stirring. All solvents and chemicals were purified on the basis
C
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Note
(250 MHz, CDCl3) δ 7.81 (d, J = 8.3 Hz, 2H), 7.30 (d, J = 8.0 Hz,
2H), 7.26−7.20 (m, 5H), 5.04 (d, J = 10.4 Hz, 2H), 4.52 (s, 2H),
4.10−3.71 (m, 4H), 2.42 (s, 3H), 1.20 (td, J = 7.1, 0.7 Hz, 6H); 13C
NMR (62.9 MHz, CDCl3) δ 215.5 (d, J = 25.4 Hz), 143.8, 136.0,
135.6, 129.4, 129.1, 128.2, 128.1, 127.8, 99.6 (d, J = 232.8 Hz), 82.6
(d, J = 11.9 Hz), 62.9 (d, J = 6.0 Hz), 53.6, 21.5, 16.1 (d, J = 6.5 Hz);
31P NMR (101.25 MHz, CDCl3) δ 10.9 HRMS (ESI) m/z [MH+]
33.1, 21.6; HRMS (ESI) m/z [MH+] calcd for C24H24NO3S 406.1471,
found 406.1465.
N-Benzyl-N-(3-hydroxy-3-phenylprop-1-ynyl)-4-methylben-
zenesulfonamide (7g). Prepared according to procedure A. Flash
chromatography: EtOAc/PE 10/90 to 50/50; orange oil, 372 mg, 24%
yield; Rf = 0.61 (EtOAc/PE = 40/60); 1H NMR (250 MHz, CDCl3) δ
7.76 (d, J = 8.3 Hz, 2H), 7.32 (d, J = 4.4 Hz, 12H), 5.49 (d, J = 5.2 Hz,
1H), 4.52 (AB syst, ΔνAB = 21.5 Hz, JAB = 14.0 Hz, 2H), 2.99 (d, J =
5.4 Hz, 1H), 2.44 (s, 3H); 13C NMR (62.9 MHz, CDCl3) δ 144.7,
140.6, 134.4, 134.2, 129.8, 128.8, 128.5, 128.4, 128.0, 127.7, 126.6,
80.0, 71.7, 64.5, 55.3, 21.6; HRMS (ESI) m/z [MH+] calcd for
C23H22NO3S 392.1315, found 392.1310.
calcd for C21H27NO5PS 436.1332, found 436.1342.
Diethyl 1-(2-Oxooxazolidin-3-yl)propa-1,2-dienylphospho-
nate (5b). Prepared according to procedure B. Flash chromatography:
EtOAc(5% NH3)/EP 60/40 to 100/0; colorless oil, 179 mg, 66%
yield; Rf = 0.20 (EtOAc); 1H NMR (360 MHz, CDCl3) δ 5.37 (d, J =
10.7 Hz, 2H), 4.25 (dd, J = 8.9, 7.0 Hz, 2H), 4.13−3.88 (m, 4H), 3.74
(td, J = 7.8, 1.0 Hz, 2H), 1.20 (t, J = 7.1 Hz, 6H); 13C NMR (90.56
MHz, CDCl3) δ 210.9 (d, J = 19.7 Hz), 155.7, 97.7 (d, J = 226.3 Hz),
84.1, 63.0 (d, J = 5.9 Hz), 62.1, 45.9, 15.9 (d, J = 6.6 Hz); 31P NMR
(101.25 MHz, CDCl3) δ 10.3; HRMS (ESI) m/z [MH+] calcd for
C10H17NO5P 262.0839, found 262.0837.
Diethyl 1-(2-Oxopyrrolidin-1-yl)propa-1,2-dienylphospho-
nate (5c). Prepared according to procedure B. The reaction was
performed in THF at −78 °C. Flash chromatography: Et2O/
MeOH(5% NH3) 98/2 to 92/8; colorless oil, 250 mg, 61% yield; Rf
= 0.24 (Et2O/MeOH(5% NH3) 95/5); 1H NMR (250 MHz, CDCl3)
δ 5.01 (d, J = 10.90 Hz, 2H), 3.77−3.65 (m, 4H), 3.22 (t, J = 7.27 Hz,
2H), 2.00−1.91 (m, 2H), 1.72−1.63 (m, 2H), 0.89 (t, J = 7.27 Hz,
6H); 13C NMR (62.9 MHz, CDCl3) δ 210.4 (d, J = 18.5 Hz), 172.8
(d, J = 4.0 Hz), 97.2 (d, J = 222.0 Hz), 82.1 (d, J = 11.9 Hz), 62.1 (d, J
= 5.3 Hz), 47.9, 29.7, 17.5, 15.3 (d, J = 6.6 Hz); 31P NMR (101.25
MHz, CDCl3) δ 10.9; HRMS (ESI) m/z [MH+] calcd for
C11H19NO4P 260.1046, found 260.1045.
Diethyl 1-(N-Benzyl-4-methylphenylsulfonamido)buta-1,2-
dienylphosphonate (8b). Prepared according to procedure B.
Flash chromatography: EtOAc/PE 20/80 to 70/30; yellow oil, 185
mg, 80% yield; Rf = 0.24 (EtOAc/PE = 50/50); 1H NMR (250 MHz,
CDCl3) δ 7.81 (d, J = 8.3 Hz, 2H), 7.34−7.15 (m, 7H), 5.45 (dq, J =
10.1, 7.4 Hz, 1H), 4.54 (s, 2H), 4.00−3.75 (m, 4H), 2.40 (s, 3H), 1.46
(dd, J = 7.4, 4.9 Hz, 3H), 1.19 (td, J = 7.1, 1.9 Hz, 6H); 13C NMR
(62.9 MHz, CDCl3) δ 212.7 (d, J = 25.4 Hz), 143.5, 136.3, 135.8,
129.3, 129.0, 128.2, 128.0, 127.6, 98.2 (d, J = 234.3 Hz), 94.2 (d, J =
12.0 Hz), 62.6 (d, J = 6.0 Hz), 53.2, 21.5, 16.1 (d, J = 6.3 Hz), 12.7 (d,
J = 4.8 Hz); 31P NMR (101.25 MHz, CDCl3) δ 11.4; HRMS (ESI) m/
z [MH+] calcd for C22H29NO5PS 450.1499, found 450.1498.
Diethyl 1-(N-Benzyl-4-methylphenylsulfonamido)-3-methyl-
buta-1,2-dienylphosphonate (8c). Prepared according to proce-
dure B. Flash chromatography: EtOAc/PE 20/80 to 100/0; white
solid, 242 mg, 72% yield; mp 86−88 °C; Rf = 0.24 (EtOAc/PE = 50/
1
50); H NMR (250 MHz, CDCl3) δ 7.80 (d, J = 8.3 Hz, 2H), 7.42−
7.06 (m, 7H), 4.56 (s, 2H), 4.03−3.63 (m, 4H), 2.38 (s, 3H), 1.50 (d,
J = 4.5 Hz, 6H), 1.16 (td, J = 7.0, 0.7 Hz, 6H); 13C NMR (62.9 MHz,
CDCl3) δ 210.5 (d, J = 25.5 Hz), 143.3, 136.8, 136.0, 129.3, 128.8,
128.1, 127.9, 127.5, 104.7 (d, J = 12.1 Hz), 95.6 (d, J = 236.0 Hz), 62.4
(d, J = 6.0 Hz), 52.9, 21.4, 19.1 (d, J = 4.6 Hz), 16.1 (d, J = 6.5 Hz).
31P NMR (101.25 MHz, CDCl3) δ 10.0; HRMS (ESI) m/z [MH+]
N-Benzyl-N-(3-hydroxybut-1-ynyl)-4-methylbenzenesulfo-
namide (7b).25 Prepared according to procedure A (1.5 g, 60%
yield).
N-Benzyl-N-(3-hydroxy-3-methylbut-1-ynyl)-4-methylben-
zenesulfonamide (7c). Prepared according to procedure A. Flash
chromatography: EtOAc/PE 10/90 to 50/50; yellow oil, 2.4 g, 92%
yield; Rf = 0.75 (EtOAc/PE = 50/50); 1H NMR (250 MHz, CDCl3) δ
7.76 (d, J = 8.3 Hz, 2H), 7.45−7.13 (m, 7H), 4.46 (s, 2H), 2.45 (s,
3H), 2.42 (s, 1H), 1.40 (s, 6H); 13C NMR (62.9 MHz, CDCl3) δ
144.7, 134.6, 134.5, 129.8, 129.1, 128.5, 128.4, 127.8, 76.2, 65.3, 55.5,
31.4, 21.7; HRMS (ESI) m/z [MH+] calcd for C19H22NO3S 344.1315,
found 344.1309.
N-Benzyl-N-[(1-hydroxycyclopentyl)ethynyl]-4-methylben-
zenesulfonamide (7d). Prepared according to procedure A. Flash
chromatography: EtOAc/PE 10/90 to 60/40; yellow oil, 1.2 g, 90%
yield; Rf = 0.62 (EtOAc/PE = 40/60); 1H NMR (250 MHz, CDCl3) δ
7.81 (d, J = 8.3 Hz, 2H), 7.38−7.27 (m, 7H), 4.51 (s, 2H), 2.49 (s,
3H), 2.35 (s, 1H), 1.91−1.57 (m, 8H); 13C NMR (62.9 MHz, CDCl3)
δ 144. 7, 134.7, 134.5, 129.7, 129.0, 128.5, 128.4, 127.8, 77.1, 75.4,
74.6, 55.5, 42.4, 23.4, 21.7; HRMS (ESI) m/z [MH+] calcd for
C21H24NO3S 370.1471, found 370.1469.
calcd for C23H31NO5PS 464.1655, found 464.1663.
Diethyl 1-(N-Benzyl-4-methylphenylsulfonamido)-2-cyclo-
pentylidenevinylphosphonate (8d). Prepared according to
procedure B. Flash chromatography: EtOAc/PE 20/80 to 80/20;
white solid, 785 mg, 74% yield; mp 64−66 °C; Rf = 0.23 (EtOAc/PE =
1
40/60); H NMR (250 MHz, CDCl3) δ 7.78 (d, J = 8.3 Hz, 2H),
7.36−7.04 (m, 7H), 4.55 (s, 2H), 3.97−3.67 (m, 4H), 2.37 (s, 3H),
2.31−2.03 (m, 4H), 1.69−1.44 (m, 4H), 1.15 (t, J = 7.1 Hz, 6H); 13C
NMR (62.9 MHz, CDCl3) δ 205.7 (d, J = 25.4 Hz), 143.2, 136.6,
136.0, 129.2, 128.8, 128.0, 127.9, 127.4, 112.9 (d, J = 12.4 Hz), 97.6
(d, J = 236.9 Hz), 62.3 (d, J = 6.0 Hz), 53.1, 31.1 (d, J = 4.0 Hz), 26.7,
21.3, 16.0 (d, J = 6.6 Hz); 31P NMR (101.25 MHz, CDCl3) δ 12.1;
HRMS (ESI) m/z [MH+] calcd for C25H33NO5PS 490.1812, found
490.1821.
Diethyl 1-(N-Benzyl-4-methylphenylsulfonamido)-3-methyl-
penta-1,2-dienylphosphonate (8e). Prepared according to proce-
dure B. Flash chromatography: EtOAc/PE 20/80 to 80/20; white
solid, 650 mg, 77% yield; mp 67−68 °C; Rf = 0.18 (EtOAc/PE = 40/
N-Benzyl-N-(3-hydroxy-3-methylpent-1-ynyl)-4-methylben-
zenesulfonamide (7e). Prepared according to procedure A. Flash
chromatography: EtOAc/PE 20/80 to 80/20; colorless oil, 699 mg,
1
60); H NMR (250 MHz, CDCl3) δ 7.93 (d, J = 8.3 Hz, 2H), 7.48−
1
90% yield; Rf = 0.73 (EtOAc/PE = 40/60); H NMR (250 MHz,
7.15 (m, 7H), 4.68 (AB syst, ΔνAB = 20.2 Hz, JAB = 15.0 Hz,, 2H),
4.14−3.77 (m, 4H), 2.49 (s, 3H), 1.96 (tq, J = 7.7, 4.2 Hz, 2H), 1.61
(d, J = 4.5 Hz, 3H), 1.28 (td, J = 7.0, 5.2 Hz, 6H), 0.92 (t, J = 7.4 Hz,
3H); 13C NMR (62.9 MHz, CDCl3) δ 210.1 (d, J = 25.5 Hz), 143.4,
137.0, 136.2, 129.4, 128.9, 128.2, 128.1, 127.6, 110.7 (d, J = 11.9 Hz),
96.8 (d, J = 235.9 Hz), 62.4, 53.0, 27.0 (d, J = 4.2 Hz), 21.6, 17.4 (d, J
= 4.8 Hz), 16.2 (d, J = 6.5 Hz), 11.5; 31P NMR (101.25 MHz, CDCl3)
δ 12.3; HRMS (ESI) m/z [MH+] calcd for C24H33NO5PS 478.1812,
found 478.1810.
CDCl3) δ 7.77 (d, J = 8.2 Hz, 2H), 7.45−7.15 (m, 7H), 4.47 (s, 2H),
2.46 (s, 3H), 2.37 (s, 1H), 1.58 (qd, J = 7.3, 3.5 Hz, 2H), 1.36 (s, 3H),
0.86 (t, J = 7.4 Hz, 3H); 13C NMR (62.9 MHz, CDCl3) δ 144.7, 134.7,
134.5, 129.8, 129.0, 128.5, 128.4, 127.8, 75.1, 68.9, 65.9, 55.5, 36.6,
29.4, 21.7, 9.0; HRMS (ESI) m/z [MH+] calcd for C20H24NO3S
358.1471, found 358.1465.
N-Benzyl-N-(3-hydroxy-3-phenylbut-1-ynyl)-4-methylben-
zenesulfonamide (7f). Prepared according to procedure A. Flash
chromatography: EtOAc/PE 20/80 to 60/40; yellow oil, 379 mg, 50%
yield; Rf = 0.53 (EtOAc/PE = 50/50); 1H NMR (360 MHz, CDCl3) δ
7.78 (dd, J = 8.4, 1.6 Hz, 2H), 7.44 (ddd, J = 6.8, 3.2, 1.6 Hz, 2H),
7.42−7.19 (m, 10H), 4.53 (AB syst, ΔνAB = 23.4 Hz, JAB = 13.6 Hz,
2H), 2.98 (d, J = 1.4 Hz, 1H), 2.46 (s, 3H), 1.67 (d, J = 1.4 Hz, 3H);
13C NMR (90.56 MHz, CDCl3) δ 145.5, 144.7, 134.4, 134.3, 129.8,
Diethyl 1-(N-Benzyl-4-methylphenylsulfonamido)-3-phenyl-
buta-1,2-dienylphosphonate (8f). Prepared according to proce-
dure B. Flash chromatography: EtOAc/PE 20/80 to 80/20; yellow oil,
404 mg, 84% yield; Rf = 0.29 (EtOAc/PE = 50/50); IR (neat) 3087,
3063, 3031, 2981, 2929, 2900, 2860, 2235, 1929, 1597, 1494, 1455
1
cm−1; H NMR (360 MHz, CDCl3) δ 7.84 (d, J = 8.1 Hz, 2H), 7.33
129.0, 128.5, 128.4, 128.1, 127.8, 127.4, 125.0, 78.6, 75.1, 70.0, 55.3,
(dd, J = 6.6, 3.0 Hz, 2H), 7.23 (td, J = 7.2, 6.8, 3.6 Hz, 8H), 7.10 (dd, J
D
dx.doi.org/10.1021/jo300790m | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Note
= 6.3, 3.1 Hz, 2H), 4.89 (AB syst, ΔνAB = 22.7 Hz, JAB = 14.7 Hz, 2H),
4.06−3.85 (m, 4H), 2.38 (s, 3H), 1.93 (d, J = 4.6 Hz, 3H), 1.21 (t, J =
7.1 Hz, 3H), 1.15 (t, J = 7.0 Hz, 3H); 13C NMR (90.56 MHz, CDCl3)
δ 213.0 (d, J = 23.6 Hz), 143.4, 136.7, 136.0, 133.3 (d, J = 5.6 Hz),
129.4, 128.9, 128.4, 128.3, 128.0, 127.7, 126.6, 109.3 (d, J = 12.2 Hz),
99.5 (d, J = 232.5 Hz), 62.8 (d, J = 7.0 Hz), 62.7 (d, J = 7.0 Hz), 52.8,
21.5, 16.2 (d, J = 7.2 Hz), 16.1 (d, J = 4.7 Hz); 31P NMR (101.25
MHz, CDCl3) δ 10.9; HRMS (ESI) m/z [MH+] calcd for
C28H33NO5PS 526.1812, found 526.1807.
N - B e n z y l - N - ( 3 - h y d r o x y - 3 - m e t h y l b u t - 1 - y n y l ) -
methanesulfonamide (10). Prepared following procedure A. Flash
chromatography: EtOAc(5% NH3)/PE 20/80 to 80/20; yellow oil, 1.1
1
g, 77% yield; Rf = 0.31 (EtOAc/PE = 50/50); H NMR (250 MHz,
CDCl3) δ 7.30−7.46 (m, 5H) 4.56 (s, 2H) 2.90 (s, 1H) 2.82−2.88 (m,
3H) 1.46 (s, 6H); 13C NMR (62.9 MHz, CDCl3) δ 134.5, 129.1,
128.8, 76.5, 75.5, 65.3, 55.5, 38.7, 31.4; HRMS (ESI) m/z [MNa+]
calcd for C13H17NO3SNa 290.0821, found 290.0825.
N-Benzyl-N-[1-(diphenylphosphoryl)propa-1,2-dienyl]-4-
methylbenzenesulfonamide (11). Prepared following procedure B.
Flash chromatography: EtOAc/PE 50/50 to 100/0; colorless oil, 140
mg, 65% yield; Rf = 0.56 (EtOAc = 100); 1H NMR (250 MHz,
CDCl3) δ 7.66 (d, J = 8.3 Hz, 2H), 7.59−7.44 (m, 6H), 7.43−7.31 (m,
4H), 7.30−7.11 (m, 7H), 4.88 (d, J = 8.7 Hz, 2H), 4.61 (s, 2H), 2.40
(s, 3H); 13C NMR (62.9 MHz, CDCl3) δ 214.9 (d, J = 22.1 Hz),
143.6, 135.7, 135.5, 132.7, 131.9, 131.8, 129.4, 129.3, 128.2, 128.0,
127.7, 103.1 (d, J = 124.4 Hz), 83.3, 53.8, 21.5; 31P NMR (101.25
MHz, CDCl3) δ 24.0; HRMS (ESI) m/z [MH+] calcd for
C29H27NO3PS 500.1444, found 500.1446.
Diethyl 1-(N-Benzyl-4-methylphenylsulfonamido)-3-phenyl-
propa-1,2-dienylphosphonate (8g). Prepared according to
procedure B. Flash chromatography: EtOAc/PE 10/90 to 50/50;
red solid, 401 mg, 88% yield; mp 39−41 °C; Rf = 0.24 (EtOAc/PE =
1
40/60); H NMR (250 MHz, CDCl3) δ 7.85 (d, J = 8.4 Hz, 2H),
7.49−7.14 (m, 10H), 6.95 (dd, J = 6.2, 2.4 Hz, 2H), 6.47 (d, J = 9.9
Hz, 1H), 4.68 (s, 2H), 4.17−3.82 (m, 4H), 2.38 (s, 3H), 1.21 (t, J =
7.0 Hz, 3H), 1.16 (t, J = 7.0 Hz, 3H); 13C NMR (62.9 MHz, CDCl3) δ
213.5 (d, J = 23.5 Hz), 143.6, 136.3, 135.8, 130.3 (d, J = 6.0 Hz),
129.4, 128.8, 128.6, 128.3, 128.0, 128.0, 127.6, 102.1 (d, J = 230.8 Hz),
101.7 (d, J = 12.1 Hz), 63.0 (d, J = 5.1 Hz), 62.9 (d, J = 5.1 Hz), 53.0,
21.4, 16.1 (d, J = 6.5 Hz); 31P NMR (101.25 MHz, CDCl3) δ 10.2;
HRMS (ESI) m/z [MH+] calcd for C27H31NO5PS 512.1653, found
512.1655.
N-(3-Hydroxy-3-methylbut-1-ynyl)-N-(4-methoxybenzyl)-4-
methylbenzenesulfonamide (12a). Flash chromatography: EtOAc-
(5% NH3)/PE 10/90 to 50/50; yellow solid, 1.7 g, 68% yield; mp
1
=56−58 °C; Rf = 0.59 (EtOAc/PE = 50/50); H NMR (360 MHz,
Diisopropyl 1-(N-Benzyl-4-methylphenylsulfonamido)-3-
methylbuta-1,2-dienylphosphonate (9a). Flash chromatography:
EtOAc(5% NH3)/PE 10/90 to 80/20; yellow oil, 134 mg, 46% yield;
Rf = 0.26 (EtOAc/PE = 30/70); 1H NMR (360 MHz, CDCl3) δ 7.85
(d, J = 9.1 Hz, 2H), 7.15−7.40 (m, 7H), 4.63 (s, 2H), 4.38−4.56 (m,
2H), 2.40 (s, 3H), 1.54 (d, J = 4.5 Hz, 6H), 1.23 (d, J = 6.1 Hz, 6H),
1.14 (d, J = 6.4 Hz, 6H); 13C NMR (90.56 MHz, CDCl3) δ 210.6 (d, J
= 26.4 Hz), 143.2, 137.2, 136.2, 129.3, 128.9, 128.2, 128.0, 127.4,
104.4 (d, J = 11.9 Hz), 97.0 (d, J = 237.8 Hz), 71.3 (d, J = 6.6 Hz),
52.8, 24.0 (d, J = 2.6 Hz), 23.7 (d, J = 5.3 Hz), 21.5, 19.1 (d, J = 5.3
Hz); 31P NMR (101.25 MHz, CDCl3) δ 10.1; HRMS (ESI) m/z
[MH+] calcd for C25H35NO5PS 492.1968, found 492.1973.
CDCl3) δ 7.76 (d, J = 8.0 Hz, 2H), 7.33 (d, J = 8.0 Hz, 2H), 7.21 (d, J
= 8.2 Hz, 2H), 6.83 (d, J = 8.1 Hz, 2H), 4.40 (s, 2H), 3.80 (s, 3H),
2.48 (s, 1H), 2.45 (s, 3H), 1.42 (s, 6H); 13C NMR (62.9 MHz,
CDCl3) δ 166.5, 159.2, 155.2, 144.4, 137.3, 129.6, 129.4, 127.8, 118.0,
113.9, 55.3, 48.5, 27.2, 21.6, 20.7; HRMS (ESI) m/z [MH+] calcd for
C20H24NO4S 374.1421, found 374.1414.
N-(3-Hydroxy-3-methylbut-1-ynyl)-4-methyl-N-phenylben-
zenesulfonamide (12c). Flash chromatography: EtOAc(5% NH3)/
PE 10/90 to 100/0; white solid, 294 mg, 40% yield; mp 100−102 °C;
Rf = 0.28 (EtOAc/PE = 20/80); 1H NMR (300 MHz, CDCl3) δ 7.58
(d, J = 8.3 Hz, 2H), 7.39−7.15 (m, 7H), 2.46 (br s, 3H), 1.96 (br s,
1H), 1.55 (s, 6H); 13C NMR (62.9 MHz, CDCl3) δ 145.2, 138.9,
132.9, 129.6, 129.2, 128.4, 128.3, 126.2, 76.4, 75.5, 65.4, 31.6, 21.8;
HRMS (ESI) m/z [MH+] calcd for C18H20NO3S 330.1158, found
330.1152.
N-Benzyl-N-[1-(5,5-dimethyl-2-oxido-1,3,2-dioxaphos-
phinan-2-yl)-3-methylbuta-1,2-dien-1-yl]-4-methylbenzene-
sulfonamide (9b). Flash chromatography: EtOAc/PE 30/70 to 100/
1
0; yellow oil, 21 mg, 7% yield; Rf = 0.65 (EtOAc/PE = 100/0); H
3-(3-Hydroxy-3-methylbut-1-ynyl)oxazolidin-2-one (12d).
NMR (250 MHz, CDCl3) δ 7.80 (d, J = 8.3 Hz, 2H), 7.39−7.22 (m,
7H), 4.63 (s, 2H), 4.15−3.61 (m, 4H), 2.42 (s, 3H), 1.56 (d, J = 4.6
Hz, 6H), 1.20 (s, 3H), 0.79 (s, 3H); 13C NMR (90.56 MHz, CDCl3) δ
210.8 (d, J = 26.5 Hz), 143.7, 137.0, 135.9, 129.6, 129.6, 128.4, 128.1,
127.8, 105.2 (d, J = 12.4 Hz), 94.2 (d, J = 232.3 Hz), 77.2 (d, J = 6.7
Hz), 53.0, 32.4 (d, J = 7.1 Hz), 22.0, 21.7, 20.9, 19.5, 19.4; 31P NMR
(101.25 MHz, CDCl3) δ 3.9; HRMS (ESI) m/z [MH+] calcd for
C24H31NO5PS 476.1655, found 476.1653.
N-Benzyl-N-[1-(5,5-dimethyl-2-oxido-1,3,2-dioxaphos-
phinan-2-yl)propa-1,2-dien-1-yl]-4-methylbenzenesulfona-
mide (9d). Flash chromatography: EtOAc/PE 30/70 to 100/0; yellow
oil, 93 mg, 33% yield; Rf = 0.24 (EtOAc/PE = 40/60); 1H NMR (250
MHz, CDCl3) δ 7.79 (d, J = 8.3 Hz, 2H), 7.41−6.82 (m, 7H), 5.10 (d,
J = 10.7 Hz, 2H), 4.57 (s, 2H), 4.03−3.67 (m, 4H), 2.42 (s, 3H), 1.20
(s, 3H), 0.80 (s, 3H); 13C NMR (62.9 MHz, CDCl3) δ 215.3 (d, J =
26.0 Hz), 143.9, 136.1, 135.4, 129.7, 129.5, 128.3, 128.1, 127.9, 98.3
(d, J = 227.9 Hz), 82.8 (d, J = 11.9 Hz), 77.4 (d, J = 6.8 Hz), 53.6, 32.4
(d, J = 7.2 Hz), 21.9, 21.6, 20.7; 31P NMR (101.25 MHz, CDCl3) δ
2.4; HRMS (ESI) m/z [MNa+] calcd for C22H26NO5PSNa 470.1162,
found 470.1160.
N-Benzyl-N-[1-(5,5-dimethyl-2-oxido-1,3,2-dioxaphos-
phinan-2-yl)-3-methylbuta-1,2-dien-1-yl]-4-methylsulfona-
mide (9e). Flash chromatography: EtOAc(5% NH3)/PE 30/70 to
90/10; white solid, 293 mg, 79% yield; mp 99−100 °C; Rf = 0.54
(EtOAc(5% NH3)/PE = 90/10); 1H NMR (250 MHz, CDCl3) δ 7.40
(dd, J = 7.9, 1.4 Hz, 2H), 7.33−7.16 (m, 3H), 4.72 (s, 2H), 3.99−3.74
(m, 4H), 2.93 (s, 3H), 1.57 (d, J = 4.6 Hz, 6H), 1.22 (s, 3H), 0.79 (s,
3H); 13C NMR (62.9 MHz, CDCl3) δ 210.4 (d, J = 27.4 Hz), 135.7,
129.2, 128.3, 127.8, 104.6 (d, J = 12.2 Hz), 93.9 (d, J = 227.4 Hz), 77.3
(d, J = 6.8 Hz), 52.8, 40.5, 32.3 (d, J = 7.1 Hz), 21.8, 20.5, 19.2 (d, J =
4.6 Hz); 31P NMR (101.25 MHz, CDCl3) δ 3.9; HRMS (ESI) m/z
[MH+] calcd for C18H27NO5PS 400.1342, found 400.1328.
Flash chromatography: EtOAc/PE 50/50 to 80/20; white solid, 77
1
mg, 21% yield; mp 84−86 °C; Rf = 0.21 (EtOAc/PE = 50/50); H
NMR (360 MHz, CDCl3) δ 4.31−4.52 (m, 2H), 3.89 (dd, J = 8.63,
7.27 Hz, 2H), 2.35 (s, 1H), 1.55 (s, 6H); 13C NMR (62.9 MHz,
CDCl3) δ 156.5, 75.8, 72.4, 65.1, 63.2, 46.8, 31.5; HRMS (ESI) m/z
[MNa+] calcd for C8H11NO3Na 192.0631, found 192.0635.
Diethyl 1-[N-(4-Methoxybenzyl)-4-methylphenylsulfonami-
do]-3-methylbuta-1,2-dienylphosphonate (13a). Flash chroma-
tography: EtOAc/PE 10/90 to 60/40; colorless oil, 201 mg, 70% yield;
Rf = 0.44 (EtOAc/PE = 80/20); 1H NMR (250 MHz, CDCl3) δ 7.83
(d, J = 8.2 Hz, 2H), 7.29 (d, J = 8.2 Hz, 2H), 7.23 (d, J = 8.7 Hz, 2H),
6.80 (d, J = 8.6 Hz, 2H), 4.52 (s, 2H), 3.99−3.85 (m, 4H), 3.77 (s,
3H), 2.42 (s, 3H), 1.56 (d, J = 4.5 Hz, 6H), 1.22 (t, J = 7.1 Hz, 6H);
13C NMR (62.9 MHz, CDCl3) δ 210.6 (d, J = 25.8 Hz), 159.1, 143.2,
137.0, 130.3, 129.3, 128.1, 127.9, 113.6, 104.6 (d, J = 12.2 Hz), 95.5
(d, J = 236.6 Hz), 62.5, 55.2, 52.5, 21.5, 19.1 (d, J = 5.1 Hz), 16.2 (d, J
= 6.7 Hz); 31P NMR (101.25 MHz, CDCl3) δ 12.1; HRMS (ESI) m/z
[MH+] calcd for C24H33NO6PS 494.1761, found 494.1754.
Diethyl 1-(N-Benzylmethylsulfonamido)-3-methylbuta-1,2-
dienylphosphonate (13b). Flash chromatography: EtOAc/PE 20/
80 to 80/20; yellow oil, 269 mg, 75% yield; Rf = 0.39 (EtOAc/PE =
1
90/10); H NMR (250 MHz, CDCl3) δ 7.30−7.06 (m, 5H), 4.57 (s,
2H), 3.96 - 3.78 (m, 4H), 2.90 (s, 3H), 1.42 (d, J = 4.4 Hz, 6H), 1.14
(t, J = 7.0 Hz, 6H); 13C NMR (62.9 MHz, CDCl3) δ 211.1 (d, J = 26.8
Hz), 135.8, 128.6, 128.1, 127.5, 103.7 (d, J = 11.9 Hz), 94.4 (d, J =
231.1 Hz), 62.3 (d, J = 6.1 Hz), 52.4, 40.0, 18.7 (d, J = 4.6 Hz), 15.9
(d, J = 6.6 Hz); 31P NMR (101.25 MHz, CDCl3) δ 12.1; HRMS (ESI)
m/z [MH+] calcd for C17H27NO5PS 388.1342, found 388.1335.
Diethyl 3-Methyl-1-(4-methyl-N-phenylphenylsulfon-
amido)buta-1,2-dienylphosphonate (13c). Flash chromatogra-
phy: EtOAc/PE 30/70 to 100/0; white solid, 41 mg, 53% yield; mp
E
dx.doi.org/10.1021/jo300790m | J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
Note
1
107−109 °C; Rf = 0.16 (EtOAc/PE = 50/50); H NMR (250 MHz,
CDCl3) δ 7.46 (d, J = 8.2 Hz, 2H), 7.27−7.37 (m, 5H), 7.22 (d, J = 8.2
Hz, 2H), 3.86−4.13 (m, 4H), 2.43 (s, 3H), 1.88 (d, J = 4.7 Hz, 6H),
1.20 (t, J = 7.0 Hz, 6H); 13C NMR (62.9 MHz, CDCl3) δ 208.17 (d, J
= 25.2 Hz), 143.5, 140.1, 136.5, 129.0, 128.9, 128.8, 128.1, 127.9,
106.2 (d, J = 12.5 Hz), 99.2 (d, J = 237.0 Hz), 62.5 (d, J = 5.0 Hz),
21.6, 19.8 (d, J = 5.0 Hz), 16.1 (d, J = 7.0 Hz); 31P NMR (101.25
MHz, CDCl3) δ 11.7; HRMS (ESI) m/z [MH+] calcd for
C22H29NO5PS 450.1499, found 450.1489.
(18) Matos, R. M.; Gomes de Lima, L. C.; de Souza, E.; Barcelos de
Souza, A. L. A.; Gomes de Lima, M. B.; Soares Raslan, D. Phosphorus,
Sulfur Silicon Relat. Elem. 2002, 177, 2859.
(19) Collins, D. J.; Drygala, P. F.; Swan, J. M. Aust. J. Chem. 1983, 36,
2517.
(20) Hamada, T.; Ye, X.; Stahl, S. S. J. Am. Chem. Soc. 2008, 130, 833.
(21) Basak, S.; Srivastava, S.; Le, N. W. J. J. Org. Chem. 1987, 52,
5095.
(22) Dooleweerdt, K.; Birkedal, H.; Ruhland, T.; Skrydstrup, T. J.
Org. Chem. 2008, 73, 9447.
(23) Chemla, F.; Dulong, F.; Ferreira, F.; Nullen, M. P.; Perez-Luna,
A. Synthesis 2011, 1347.
(24) Yao, B.; Liang, Z.; Niu, T.; Zhang, Y. J. Org. Chem. 2009, 74,
4630.
Diethyl 3-Methyl-1-(2-oxooxazolidin-3-yl)buta-1,2-dienyl-
phosphonate (13d). Flash chromatography: EtOAc(5% NH3)/PE
30/70 to 100/0; colorless oil, 34 mg, 26% yield; Rf = 0.20 (EtOAc(5%
1
NH3)/PE = 90/10); H NMR (400 MHz, CDCl3) δ 4.36 (t, J = 7.9
Hz, 2H), 4.20−4.12 (m, 4H), 3.88 (t, J = 7.8 Hz, 2H), 1.89 (d, J = 4.9
Hz, 6H), 1.34 (t, J = 7.0 Hz, 6H); 13C NMR (90.56 MHz, CDCl3) δ
205.4 (d, J = 20.3 Hz), 156.4, 106.4 (d, J = 8.3 Hz), 94.8 (d, J = 232.5
Hz), 63.0 (d, J = 4.6 Hz), 62.1, 46.3, 20.0 (d, J = 5.3 Hz), 16.3 (d, J =
6.6 Hz); 31P NMR (101.25 MHz, CDCl3) δ 11.5; HRMS (ESI) m/z
[MH+] calcd for C12H21NO5P 290.1152, found 290.1144.
(25) Barbazanges, M.; Meyer, C.; Cossy, J.; Turner, P. Chem.Eur. J.
2011, 17, 4480.
ASSOCIATED CONTENT
■
S
* Supporting Information
1H and 13C NMR spectra for all new compounds. This material
is available free of charge via the Internet at http://pubs.acs.
org/.
AUTHOR INFORMATION
Corresponding Author
*E-mail: nicolas.rabasso@u-psud.fr.
■
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
We thank the University Paris-Sud and the CNRS for financial
support.
■
REFERENCES
■
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dx.doi.org/10.1021/jo300790m | J. Org. Chem. XXXX, XXX, XXX−XXX