Asymmetric oxidation of sulfenates to sulfinates as a new route to optically active ortho-phosphorylated phenyl sulfoxides

Article abstract of DOI:10.1016/j.tetasy.2005.09.005

An asymmetric synthesis of benzenesulfinates bearing a phosphonate group at the ortho-position, based on the diastereoselective oxidation of the corresponding sulfenates, has been developed. For this purpose, a number of sulfenates were prepared in high yields by TFFA-promoted condensation of different chiral alcohols with a suitable sulfenyl chloride precursor. Diastereomeric excesses were determined by ³¹P NMR spectroscopic data with the configuration of the newly created stereogenic centre being assigned through correlation and chemical studies. A practical synthesis of both enantiomers of diisopropyl (2-methylsulfinyl)phenylphosphonate 6 in enantiomeric excess close to 85% is also presented.

Full text of DOI:10.1016/j.tetasy.2005.09.005

Tetrahedron:
Asymmetry
Tetrahedron: Asymmetry 16 (2005) 3406–3415
Asymmetric oxidation of sulfenates to sulfinates as a new route
to optically active ortho-phosphorylated phenyl sulfoxides
Matthieu Hamel,a Guillaume Grach,a Isabelle Abrunhosa,a Mihaela Gulea,a
b,
b
Serge Masson,a Michel Vazeux,a,* Jozef Drabowicz and Marian Mikolajczyk
*
aLaboratory of Molecular and Thio-Organic Chemistry (UMR CNRS 6507), ENSICAEN—University of Caen, 6,
Bd Mare´chal Juin, 14050 Caen, France
bCentre of Molecular and Macromolecular Studies, Polish Academy of Sciences, Department of Heteroorganic Chemistry,
Sienkiewicza 112, 90-363 Lodz, Poland
Received 25 August 2005; accepted 7 September 2005
Available online 18 October 2005
Abstract—An asymmetric synthesis of benzenesulfinates bearing a phosphonate group at the ortho-position, based on the diastereo-
selective oxidation of the corresponding sulfenates, has been developed. For this purpose, a number of sulfenates were prepared in
high yields by TFFA-promoted condensation of different chiral alcohols with a suitable sulfenyl chloride precursor. Diastereomeric
excesses were determined by 31P NMR spectroscopic data with the configuration of the newly created stereogenic centre being
assigned through correlation and chemical studies. A practical synthesis of both enantiomers of diisopropyl (2-methylsulfinyl)phen-
ylphosphonate 6 in enantiomeric excess close to 85% is also presented.
ꢀ 2005 Elsevier Ltd. All rights reserved.
O
P
1. Introduction
O
P
Ph
OH
OH
OEt
OEt
P
Ph
Ar
Difunctionalized phosphorus and sulfur organic com-
pounds have been recognized not only as useful syn-
thetic intermediates,1 but also as biologically relevant
materials.2 Due to their chelating features, they have
been employed as ligands for transition metal complexes
and in various catalytic processes.3 Representative
examples related to this workinclude the ortho-sulfanyl-
phenylphosphonic acid I and its methyl sulfide deriva-
tive II. The former has been found active as a metallo-
phosphatase inhibitor4 while the latter has been involved
in the preparation of a new class of platinum(II) com-
plexes5 designed for the treatment of solid tumours
(Fig. 1). In a recent study by Natile et al., the a-sul-
finylphosphonate ligand III was shown to act as an
O,S-donor towards platinum.6 On the other hand, Hiroi
et al. demonstrated the usefulness of chiral aromatic
sulfoxide ligands IV appended with a phosphano func-
tionality in a Tsuji–Trost allylation reaction (ee up to
85%).7
S
S
SR
I : R = H
II: R = Me
R
O
O
III
IV
Figure 1.
Over the past few years, we have taken much interest in
the design of aromatic chiral ligands possessing spatially
proximate stereodefined P and/or -S atom centres.
To this end, some of us developed an efficient method
for the large scale preparation of (2-alkylsulfanyl)phen-
ylphosphonic acid diesters and related P-stereogenic
phenylphosphonamides. The synthesis is based on the
ortho-lithiation of an aryl phosphorothioate or phos-
phorodiamidothioate, followed by migration of the
phosphorylated moiety from sulfur to carbon.8,9 To
extend further the potential of this synthetic protocol
and in view of the increasing importance of mixed P,S-
containing compounds in coordination chemistry, we
have recently focused special attention on the synthesis
of optically active sulfoxide derivatives in both series.
There are currently many methods for obtaining chiral
*
Corresponding authors. Fax: +33 (0)2 31 45 28 77 (M.V.); e-mail
addresses: draj@bilbo.cbmm.lodz.pl; michel.vazeux@ensicaen.fr
0957-4166/$ - see front matter ꢀ 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tetasy.2005.09.005

M. Hamel et al. / Tetrahedron: Asymmetry 16 (2005) 3406–3415
3407
sulfoxides.10 Among them, the resolution of a 2-sulfinyl-
ated phenylphosphonic acid monoester only gave us
one enantiomerically pure sulfoxide.11 As summarized
in Scheme 1, the direct enantioselective oxidation of
o-phosphonophenyl sulfides achieved under catalytic
or stoichiometric conditions was found to occur with
low to moderate selectivity. Moreover, studies on the
diastereoselective oxidation of phenylsulfides which bear
a defined chiral phosphonamido group9,12 at the ortho-
position (derived from trans-N,N0-dimethylcyclohex-
ane-1,2-diamine), have shown that diastereoselection
is variable, depending on the nature of the oxidizing
reagent. In particular, the replacement of achiral oxi-
dants by homochiral ones, such as DavisÕ oxaziridines,
increases the diastereomeric excess from 15–26% up to
82%.
only a few examples dealing with the oxidation of sulfe-
nates. Kagan et al. reported that the modified Sharpless
chiral titanium reagent was able to give optically active
sulfinates with enantiomeric excesses up to 36%.15 The
self-photoinduced singlet oxygen and m-chloroperoxy-
benzoic acid oxidations of sec-alkyl 4-nitrobenzenesulfe-
nates were each only slightly diastereoselective.16 It is
worth mentioning that extension of this stereoselec-
tive oxidation to sulfenamides, that is, N-sulfenyloxazo-
lidinones, has been successfully used by Evans to
produce chiral sulfoxides in high enantioselectivities.17
Herein, we describe the diastereoselective oxidation of
enantiopure o-(O-diisopropylphosphonyl)benzenesulfe-
nates derived from various chiral alcohols and a suitable
sulfur precursor.
2. Results and discussion
O
P
O
P
R'
R'
R'
chiral
oxidant
At first, we investigated the formation of diastereomeric
O-menthyl benzenesulfinates 3 (Scheme 2) in a Phillips-
type synthesis.13a,c,18 Accordingly, the ortho-mercapto
phenyl-phosphonate 1 was initially converted into its
sulfinyl chloride 2, which could be further esterified
without isolation by (ꢀ)-menthol using pyridine as base
in ether to afford the desired sulfinate esters 3 in good
yield but poor selectivity (33% de). Additionally, 3 are
oils and attempts to separate both epimers failed.
R'
*
R
SR
S
ee:13-73%
de: 82%
R' = OMe, OiPr
R'-R' = chiral diamine
O
Scheme 1.
Taking into account these not fully satisfactory results
we considered to study AndersenÕs approach, (the reac-
tion of a chiral sulfinate and an organometallic reagent
with inversion of the configuration at the sulfur atom),13
for the preparation of optically active phenylsulfoxides
bearing an ortho-phosphonate group. While several dia-
stereoselective methods exist for the generation of sulfi-
nate esters from sulfinyl chlorides and chiral alcohols,14
the possibility of employing enantiopure sulfenates for
their synthesis appealed to us as an alternative and inter-
esting approach. To the best of our knowledge, there are
Therefore, the objective herein was to prepare optically
active ortho-phosphonylated benzenesulfenates derived
from chiral alcohols and to workup oxidizing proce-
dures through which the required diastereomeric sulfi-
nates would be accessible with high diastereomeric
excesses and chemical yields. (1R,2S,5R)-Menthyl benz-
enesulfenate 5 was chosen as the first candidate for these
investigations (Scheme 3). Thus, chlorination of thiol 1
O
O
O
P
(OiPr)
Cl
(OiPr)
P
(OiPr)
P
2
2
2
M*OH, Py
de = 33 %
(CH3CO)2O
Cl2
OM*
*
S
S
SH
O
1
2
72% yield
3a / 3b
ratio 2:1
O
M*OH = (1R,2S,5R)-Menthol
Scheme 2.
O
P
O
(OiPr)
Cl
1) THF, M*OH, rt
0.1 eq. TFAA
2
P
(OiPr)2
OM*
SO2Cl2
CH2Cl2
1
2) -78˚C, NEt3
S
S
4
5
83%
M*OH = (-)-Menthol
O
P
O
(OiPr)2
OM*
P
(OiPr)2
Me
MeMgBr
Et2O
oxidant
solvent
5
*
*
S
S
O
O
78%
3a / 3b
(-)-6 / (+)-6
Scheme 3.

3408
M. Hamel et al. / Tetrahedron: Asymmetry 16 (2005) 3406–3415
with sulfuryl chloride furnished 4. Sulfenyl chloride 4
was condensed with (ꢀ)-menthol at 0 ꢁC in the presence
of Et3N as previously described for the preparation of
alkyl benzenesulfenates19 to provide the desired sulfe-
nate 5, although, in only 20% yield.
mixture; the downfield diastereomeric peakrepresents
isomer 3a, while the upfield signal refers to 3b (14.13
and 13.95 ppm, respectively).
The reaction of sulfenate 5 with mCPBA gave sulfinates
3 in 97% yield with a diastereomer ratio of only 56:44
(entry 1). The use of N-haloamides as oxidants, which
is well established for the conversion of sulfides into sulf-
oxides,20 provided higher des ranging from 40% to 76%
(entries 2–5). Oxidations are nearly complete within
15 min and N-bromosuccinimide (NBS) is clearly the
oxidant of choice in terms of selectivity. It should be
pointed out that, compared to the peracid oxidation,
these halogen-mediated oxidations carried out in aque-
ous media (THF or CH3CN/H2O) occurred with an
opposite diastereoselectivity, 3b being the major isomer.
This stereochemical outcome can be rationalized by ref-
erence to a two-step mechanism. In agreement with the
literature reports dealing with the hydrolysis of (acyl-
amino) and (alkoxy)sulfonium salts,21 we can reason-
ably speculate that the haloamide mediated oxidation
of sulfenate 5 proceeds via the formation of an (alk-
oxy)halosulfonium cation, followed by mild deplace-
ment of the S–X bond with a molecule of water,
causing inversion of configuration at the sulfur.
In search of more efficient conditions, we found that the
yield was dramatically improved when a catalytic
amount (0.1 equiv) of trifluoroacetic anhydride (TFAA)
was used as a chemical promoter. In agreement with this
result, the overall nucleophilic substitution on sulfenyl
chloride 4 can be confidently assumed to follow Scheme
4. According to this scheme, TFAA should give rise to a
sulfenyl trifluoroacetate, a more reactive species for
displacement by an alcohol. As outlined in the catalytic
cycle, the generated triethylammonium trifluoroacetate
salt can be viewed as being capable of acting also as a
catalyst for the overall process. This hypothesis has been
fully checked in separate experiments. On the other
hand, it is noteworthy that the intermediate sulfenyl
chloride 4 was easily generated and directly used with-
out isolation and purification through the first reaction
sequence outlined in Scheme 3.
ArSCl + ε (CF3CO)2O
4
The data presented in Table 1 also show that the two
enantiomers of commercially available (8,8-dichloro-
camphorylsulfonyl)oxaziridine, noted here (ꢀ)-Ox and
(+)-Ox, afforded the ÔmatchedÕ pair of diastereomers
3a and 3b (66% de) and the ÔmismatchedÕ pair (40%
de), respectively. This effect is accompanied by an inver-
sion of the configuration at sulfur, demonstrating that
the asymmetric induction is due mainly to the incoming
chiral oxaziridine and not to the menthyl group of a
sulfenate. Obviously, it is reasonable to expect that the
de values of sulfinates formed by oxidation of sulfenates
depend on the bulkiness of the alkoxy moiety. Along
this line, we briefly examined the reaction between the
achiral O-methyl 2-(diisopropylphosphoryl)benzenesul-
fenate 7 and the (ꢀ)-Ox, which was found to give the
corresponding sulfinate ester 8 but with only 20% ee.
In addition, the oxidation with oxaziridines requires
long completion times and the formation of a sulfon-
imine by-product makes the purification procedure less
convenient. As already pointed out, oily O-menthyl ben-
zenesulfinates 3a and 3b could not be separated as pure
diastereomers by flash chromatography.
CF3CO2M*
M*OH
Et3N
+
CF3COCl
HEt3N+Cl-
HEt3N+Cl-
M*OH
ArS OCOCF3
/ Et3N
CF3COO- HEt3N+
ArSOM*
ArSCl
4
5
Scheme 4.
We next examined the reaction of the enantiopure men-
thyl benzenesulfenate 5 with some achiral and chiral oxi-
dizing agents. The main results of this diastereoselective
oxidation leading to epimeric sulfinates 3a and 3b are
collected in Table 1. The extent of asymmetric induction
in the formation of sulfinate esters 3 was determined by
analysis of the 31P NMR spectra of the crude reaction
Table 1. Oxidation of (1R,2S,5R)-(ꢀ)-menthyl benzenesulfenate 5 into epimeric sulfinates 3
Entry
Oxidanta
Solvent/temperature (ꢁC)/time
Yieldb (%)
Diastereomeric ratioc 3a/3b
de (%)
1
2
3
4
5
6
7
mCPBA
NCS
NIS
N-BPT
NBS
CH2Cl2/ꢀ78 to 0/1 h
THF–H2O/rt/15 min
MeCN–H2O/rt/15 min
MeCN–H2O/rt/15 min
MeCN–H2O/rt/15 min
CCl4/rt/4 days
97
95
88
92
95
65
65
56/44
30/70
23/77
17/83
12/88
17/83
70/30
12
40
54
66
76
66
40
(ꢀ)-Ox
(+)-Ox
CCl4/rt/4 days
a N-Bromophthalimide (N-BPT). (8,8-Dichlorocamphorylsulfonyl)-oxaziridine noted (+) and (ꢀ)-Ox.
b Isolated yield of purified products for a complete reaction.
c Diastereomeric ratio based on 31P NMR of the crude mixture, epimer a having the downfield signal.

M. Hamel et al. / Tetrahedron: Asymmetry 16 (2005) 3406–3415
3409
In order to determine the configuration of the newly cre-
ated stereogenic sulfinyl centre in menthyl sulfinate 3,
the diastereomerically enriched mixture with a 76% de
and {[a]D = +10 (c 1.0, CHCl3)} (Table 1, entry 5)
was treated with methylmagnesium bromide to afford,
Previous workon the asymmetric synthesis of menthyl
sulfinates from sulfinyl chlorides and (ꢀ)-menthol under
classical conditions has established that the (+)-diaste-
reomer produced, invariably had an (R)-configuration
at sulfur.23
as expected, optically active methyl sulfoxides
6
with 76% ee (measured by HPLC analysis on a chiral
column and 1H NMR with (R)-(+)-t-butyl-phen-
ylphosphinothioic acid22). Comparing the sign of the
specific rotation of o-(O-diisopropylphosphonyl)phenyl
methyl sulfoxide 6 {[a]D = ꢀ116 (c 0.55, CHCl3)} with
the one provided in the literature for enantiopure (R)-
(2-methylsulfinyl)phenylphosphonic dimethyl ester
([a]D = +150.7),11 we were able to assign the (S)-abso-
lute configuration to the sulfoxide enantiomer (ꢀ)-6. It
follows that the major dextrorotatory diastereomer 3b
formed in the asymmetric oxidation of (ꢀ)-menthyl sul-
fenate 5 with NBS has an (R)-configuration at the sul-
fur. It should be pointed out that the epimer with the
(S)-configuration at sulfur was found to predominate
over the other epimer in the reaction of sulfinyl chloride
2 with (ꢀ)-menthol from an analysis of the 31P NMR
spectrum of a mixture 3a/3b equals to 2:1 (Scheme 2).
The above results encouraged us to extend this new
asymmetric oxidation of sulfenates by using chiral alco-
hol inductors other than (ꢀ)-menthol. They include:
8-phenylmenthol, (1R,2S)-(ꢀ)-trans-2-phenylcyclohexa-
nol,24 borneol,25 diacetone-D-glucose26 and (R)-1-
(2,4,6-triisopropylphenyl)ethanol.27 Most of them were
chosen on the basis of established useful protocols for
sulfinate syntheses starting from sulfinyl chlorides. By
applying the TFAA-induced condensation of sulfenyl
chloride 4 with these alcohols according to Scheme 3,
enantiomerically pure benzenesulfenates 9–13 were rou-
tinely formed in yields ranging from 80% to 85% after
purification. Their reactions with enantiopure oxaziri-
dines as well as NBS or mCPBA were then examined.
The chemical yields and diastereomeric excess values
of the corresponding sulfinate esters 14–18, together
with other experimental data are collected in Table 2.
Table 2. Stoichiometric oxidation of chiral benzenesulfenates 9–13 into the corresponding epimeric sulfinates 14–18
O
P
O
P
(OiPr)2
OR*
(OiPr)2
OR*
THF, 0.1 eq TFAA
R*OH / NEt3
oxidant
solvent
4
*
S
S
14-18
9-13
O
O
O
O
HO
O
R*OH =
HO
Ph
HO
OH
Ph
O
HO
(-)-8-phenyl-
menthol
trans-2-phenyl-
cyclohexanol
(R)-Greene's alcohol
(-)-Borneol
diacetone-D-
glucose
Sulfenates :
Sulfinates :
9
10
15
11
16
12
17
13
18
14
Entry Chiral sulfenatea Oxidant
Solventb/T ꢁC/time
Sulfinate Yieldc (%) Diastereomeric 31P NMRe a/b de (%)
epimers
ratiod a/b
1
2
3
4
5
6
7
8
9
9
NBS
MeCN–H2O/rt/10 min 14
70
79
85
67
76
92
84
94
65
74
95
77
85
17.5/82.5
92.5/7.5
9/91
87/13
42/58
62.5/37.5
45/55
22.5/77.5
23/77
27/73
69/31
65
85
82
74
16
25
10
55
54
46
38
9
(+)-Ox
(ꢀ)-Ox
NBS
(+)-Ox
NBS
(ꢀ)-Ox
mCPBA
NBS
CCl4/rt/10 days
CCl4/rt/10 days
MeCN–H2O/rt/1 h
CCl4/rt/4 days
14
14
15
15
13.39/13.18
9
10
10
11
11
12
12
12
13
13
13
13.04/12.95
12.54/12.51b
13.06/12.99
MeCN–H2O/rt/10 min 16
CCl4/rt/8 days
16
17
17
17
18
18
18
CH2Cl2/ꢀ78 to 0/1 h
9
MeCN/H2O/rt/1 h
12.29/12.11
13.09/12.90
10
11
12
13
(+) or (ꢀ)-Ox CCl4/rt/12 days
mCPBA
(+)-Ox
(ꢀ)-Ox
THF/ꢀ78 to 0/1 h
CCl4/rt/10 days
CCl4/rt/7 days
54.5/45.5
7/93
86
a Substrate concentrations were about 0.05 M in all solvents. MeCN–H2O (2:1 v/v).
b 31P NMR spectrum taken in MeOD in entry 5.
c Isolated yield after purification.
d The diastereomeric ratio was determined by 31P NMR spectral analysis at 400 MHz in CDCl3 of the crude reaction products.
e In each case, epimer a has a downfield shift of the 31P NMR resonance.

3410
M. Hamel et al. / Tetrahedron: Asymmetry 16 (2005) 3406–3415
These compounds, easily characterized by 31P NMR
spectroscopy, usually absorb upfield from their dicoor-
dinate sulfenates. As a general trend, the sulfenates,
which were less stable than the sulfinates, can be stored
under argon in a refrigerator for over one month with
essentially no decomposition. Moreover, to reach com-
pletion for the oxidation, it tookseveral days with oxaz-
iridines while it tookonly a few minutes to 1 h with NBS
or mCPBA.
3. Conclusion
We have reported that the oxidation of various phos-
phorus-based enantiopure benzenesulfenates with achi-
ral and chiral reagents takes place under mild
conditions to yield the corresponding sulfinates in high
chemical yields. (ꢀ)-Menthol and trans-2-phenylcyclo-
hexanol were found to be the most efficient auxiliaries
using NBS as oxidant regarding diastereomeric excess
(76% and 74%, respectively). The oxidation of 8-phenyl-
menthyl sulfenates with DavisÕ oxaziridines allows a
practical synthesis of both enantiomers of diisopropyl
2-(methylsulfinyl)phenylphosphonate 6 in nearly 85%
ee. DAG and GreenÕs alcohol derivatives were simi-
larly oxidized with variable diastereoselectivity. Efforts
to optimize the procedure and extend the oxidation
protocol to other types of derivatives are currently
underway.
The oxidation of chiral benzenesulfenates 9–13 produces
a mixture of epimeric sulfinates 14–18 in good yields.
The diastereomeric ratios of the sulfinate esters is found
to be strongly dependent on the structure of substrates
and again sensitive to the oxidizing reagent used. Thus,
the NBS-mediated oxidation of (1R,2S,5R)-8-phenyl-
menthyl sulfenate 9 proceeded with significantly lower
diastereoselectivity (Table 2, entry 1, 65% de) than the
corresponding process with the parent menthyl com-
pound 5 (Table 1, entry 5, 76% de). If we assume that
the direction of the asymmetric oxidation is not really
affected by the remote phenyl group on the chiral
moiety, the major epimer 14b formed should have the
(R)-configuration at sulfur. Unexpectedly, the diastereo-
selectivity of the oxidation is reversed when using the
sulfenate ester of (1R,2S)-trans-2-phenylcyclohexanol
10 with NBS providing preferentially the sulfinate
epimer 15a with 74% de (Table 2, entry 4). The sense
of asymmetric induction is also inverted with (+)-Ox
as seen in entry 5, compared to the result obtained in
entry 2. We have no explanation at this time to account
for the observed selectivity in the formation of 15. More
importantly, epimeric phenylmenthyl sulfinates 14a and
14b were produced with a good level of diastereocontrol
using chiral oxaziridines (+)-Ox and (ꢀ)-Ox (entries 2
and 3, respectively). This suggests that the method
developed herein is almost practically useful for the
synthesis of phenylsulfoxide enantiomers appended with
a 2-phosphonyl group. In contrast, the oxidation of
bornyl sulfenate 11 by (ꢀ)-Ox occurred in an essentially
stereorandom fashion (10% de, entry 7). Interesting
results were obtained with the DAG benzenesulfenate
ester 12. Accordingly, 12 was converted into the corre-
sponding sulfinates 17a and b having nearly similar
diastereomer ratio by reaction with either mCPBA,
NBS or chiral oxaziridines (entries 8–10, 55–46% de),
17b being the major diastereomer formed whatever the
oxidant used. Although the diastereoselection was some-
what modest, we were pleased to isolate the major
epimer as a white solid in a diastereomerically pure state
by a single recrystallization from ether/pentane (1:2,
v/v) with a recovery of 46%. Efforts to obtain suitable
crystals of 17b for X-ray analysis are currently in pro-
gress. The last two entries also show that the oxidation
with (+)-Ox of sulfenate 13, derived from the GreeneÕs
alcohol, proceeded in the mismatched manifold to afford
a diastereomeric mixture of sulfinates 18a,b in a 55/45
ratio. The reaction of (ꢀ)-Ox with 13, which occurred
in the matched manifold, gave sulfinate 18b as a major
epimer. Furthermore, since the reaction of this latter
diastereomeric mixture with methylmagnesium bromide
gave sulfoxide 6 with [a]D = ꢀ145.2 (CHCl3), 18b was
concluded to have an (R)-configuration at sulfur.
4. Experimental
4.1. General
Reactions were carried out under a nitrogen or
argon atmosphere. THF was purified with a PURE-
SOLVTM apparatus developed by Innovative Technol-
ogy Inc. Et3N was distilled over CaH2. CCl4 was
distilled over P2O5 and stored over CaCl2 under a
nitrogen atmosphere. The synthesis of diisopropyl 2-
(sulfanyl)phenylphosphonate
1 has been described
previously.11
NMR spectra were recorded in CDCl3, unless other-
wise stated, on Bruker spectrometers at 250, 400 or
¨
500 MHz. Chemical shifts d were indicated in ppm
using TMS as the internal standard or H3PO4 as the
external standard for 31P NMR spectra. Coupling con-
stants J are given in hertz (Hz). 13C {1H} NMR spectra
were recorded at 62.9, 100.6 or 125.7 MHz and 31P
{1H} NMR spectra at 101.2, 161.9 or 202 MHz. Mass
spectra were obtained on a GC/MS Saturn 2000 or on
a Waters QTOF micro. Optical rotation values were
measured on a Perkin–Elmer 241 automatic polari-
meter. IR spectra were recorded with a Perkin–Elmer 16
PC FT-IR instrument. Satisfactory analytical data were
obtained using a THERMOQUEST NA 2500 instru-
ment. Thin layer chromatography (TLC) were
performed on silica gel 60 F254, with UV or 5% potas-
sium permanganate solution detections. Flash chroma-
tography was achieved on silica gel columns (40–
63 lm) using nitrogen pressure. HPLC analysis of
mixture of enantiomeric sulfoxides 6 was performed
on a Column Daicel ChiralpakAD-H 250 mm
·
4.6 mm · 5 lm. Flow: 1 mL/min. Column tempera-
ture: 20 ꢁC. Eluent 80% n-heptane/20% propanol-2,
PDA 207.0 nm, t0 = 3.34 min; ta = 5.53 min; tb =
7.55 min.
Numeral identifications of carbon atoms for compounds
listed above are arbitrary and given only for helping the
description of NMR spectra.

M. Hamel et al. / Tetrahedron: Asymmetry 16 (2005) 3406–3415
3411
(O)n
S
1.61–1.70 (m, 2H); 2.33–2.45 (m, 2H); 3.48 (dt, 1H,
O
S
3
6
3JHH = 4.1, JHH = 10.7); 4.61–4.78 (m, 2H); 7.14 (ddt,
3
6
3
3
6
2
S
2
4
5
4
5
2
4
5
Cl
O
OR*
3
4
4
CH3
O
1
1H, JHH = 7.4, JHH = 1.0, JHP = 3.3); 7.45–7.49 (m,
1
1
O
1H); 7.65–7.79 (m, 2H). 31P NMR (101.2 MHz): d
16.4. C NMR (62.9 MHz): d 16.6 (s, C9 ); 21.7 (s,
P
P
P
O
O
O
13
O
O
0
O
3
0
0
0
C9 ); 22.7 (s, C7 ); 23.8 (s, C3 ); 24.3 (d, J = 3.2, CH3);
3
0
0
24.7 (d, J = 3.9, CH3); 26.0 (s, C8 ); 32.4 (s, C4 ); 34.8
4
n = 0: 5; 7; 9-13
n = 1: 3; 8; 14-18
6
(s, C5 ); 41.5 (s, C6 ); 49.6 (s, C2 ); 71.8 (d, 2J = 5.0,
0
0
0
2
7'
0
CH); 71.9 (d, J = 4.8, CH); 87.6 (s, C1 ); 122.2 (d,
7'
1J = 189.9, C1); 122.9 (d, J = 13.2, C5); 125.5 (d, J =
13.2, C3); 132.5 (d, 4J = 3.1, C4); 134.0 (d, 2J = 8.8,
C6); 149.5 (d, 2J = 10.1, C2). IR (NaCl) cmꢀ1: 2955;
2870; 1580; 1450; 1424; 1385; 1373; 1250 (mP@O);
1103; 980 (mP–O); 764 (mS–O). MS m/z (%): 429
(MH+; 58); 290 (100); 273 (31); 249 (33); 206 (95); 189
(99); 136 (12). Analysis for C22H37O4PS: calculated (C:
61.66; H: 8.70); found (C: 61.40; H: 9.04).
3
3
3''
5'
5'
6'
4'
6'
1'
4''
2''
1''
4'
3'
3'
6'
1'
3'
2'
1'
4'
5'
HO
HO
2'
2'
2''
1''
3''
4''
8'
8'
HO
9'
9'
1'
2'
8'
6'
7'
O
9'
8'
HO
7'
1'
2'
3'
4'
3'
O
6'
8'
6'
O
10'
O
5'
5'
1'
9'
7'
9'
4.2.3. Methyl 2-(diisopropylphosphoryl)benzenesulfenate
5'
4'
4' O
2' OH
3'
HO
1
10'
7. Yield 87%. Colourless liquid. H NMR (250 MHz):
d 1.23 (d, 6H, 3JHH = 6.2); 1.38 (d, 6H, 3JHH = 6.2); 3.78
3
3
4.2. Typical procedure for the synthesis of sulfenates
(s, 3H); 4.67 (dsept, 2H, JHH = 6.2, JHP = 7.8); 7.14–
7.21 (m, 1H); 7.49–7.59 (m, 2H); 7.70–7.78 (m, 1H). 31P
NMR (101 MHz): d 16.6. 13C NMR (62.9 MHz): d 24.0
(d, 3J = 4.8, CH3); 24.4 (d, 3J = 3.9, CH3); 65.4 (s, CH3–
To a stirred solution of diisopropyl 2-(sulfanyl)-phen-
ylphosphonate 1 (2 g, 7.29 mmol) in dichloromethane
(20 mL) was slowly added sulfuryl chloride (0.76 mL,
9.48 mmol) under nitrogen flow. The solution was stir-
red for 30 min at room temperature. After evacuation
of the solvent and gases, THF (25 mL) was added
followed by menthol (1.140 g, 7.29 mmol) and trifluoro-
acetic anhydride (103 lL, 0.73 mmol). After cooling to
ꢀ78 ꢁC, triethylamine (2.03 mL; 14.6 mmol) was added.
The reaction mixture was allowed to reach room tem-
perature, stirred for one another hour and then hydro-
lyzed with a 5% solution of H2SO4. The aqueous layer
was extracted with diethyl ether. The combined extracts
were washed successively with a 5% solution of K2CO3
and brine, dried over MgSO4 and concentrated. The
resulting oil was purified by silica gel chromatography
with pentane–ethyl acetate as eluent to yield enantio-
pure menthyl sulfenate 5 in 83% yield.
2
3
O); 71.7 (d, J = 5.3 Hz, CH); 120.6 (d, J = 13.2, C5);
122.2 (d, 1J = 189.3, C1); 124.5 (d, 3J = 13.2, C3);
132.8 (d, 4J = 2.5, C4); 134.0 (d, 2J = 8.8, C6); 147.9
2
(d, J = 10.7, C2). IR (NaCl) cmꢀ1: 2977; 2931; 1580;
1449; 1423; 1385; 1374; 1245 (mP@O); 1143; 1102; 987
(mP–O); 760 (mS–O). GC/MS m/z (%): 305 (MH+; 48);
304 (M+; 100); 274 (24); 273 (74); 206 (95); 190 (45);
189 (82). Analysis for C13H21O4PS: calculated (C:
51.30; H: 6.95); found (C: 51.00; H: 6.82).
4.2.4. L-8-Phenylmenthyl 2-(diisopropylphosphoryl)benz-
enesulfenate 9. Yield 81%. White solid. Mp: 71 ꢁC.
1
[a]D = +40.0 (c 0.5, CHCl3). H NMR (400 MHz): d
3
0.66–1.14 (m, 3H); 0.78 (d, 3H, JHH = 6.5); 1.23 (d,
3
3
3H, JHH = 6.2); 1.25 (d, 3H, JHH = 6.2); 1.22–1.61
3
(m, 3H); 1.42 (d, 3H, JHH = 5.6); 1.44 (d, 3H,
3JHH = 5.9); 1.47 (s, 3H); 1.58 (s, 3H); 1.92–1.98 (m,
3
This procedure was extended to the synthesis of sulfe-
nate esters 9–13 with chemical yields ranging from
75% to 85%.
1H); 2.09–2.18 (m, 1H); 3.65 (dt, 1H, JHH = 10.4,
3JHH = 6.8); 4.70 (dsept, 2H, JHP = 6.0, JHH = 6.2);
3
3
7.10–7.21 (m, 2H); 7.27–7.40 (m, 4H); 7.46 (t, 1H,
3
3JHH = 7.4); 7.56 (m, 1H, JHH = 7.8); 7.72 (ddt, 1H,
4.2.1. Diisopropyl 2-(chlorosulfinyl)phenylphosphonate
3JHH = 7.2, 3JHP = 13.4, 4JHH = 1.3). 31P NMR
(162 MHz): d 15.8. 13C NMR (100.6 MHz): d 22.4 (s,
4. Conversion: 100%. Orange liquid. 1H NMR (250
3
3
3
3
0
MHz): d 1.16 (d, 6H, JHH = 6.2); 1.31 (d, 6H, JHH
=
C7 ); 24.1 (d, J = 4.5, CH3); 24.2 (d, J = 4.4, CH3);
3
3
0 0 0 0
24.5 (s, C9 ); 25.1 (s, C9 ); 28.0 (s, C3 ); 30.3 (s, C5 );
6.2); 4.68 (dsept, 2H, JHH = 6.2, JHP = 8.8); 7.21–7.31
(m, 1H); 7.46–7.57 (m, 1H); 7.57–7.82 (m, 2H). 31P
NMR (101 MHz): d 17.4. 13C NMR (62.9 MHz): d 24.0
(d, 3J = 5.0, CH3); 24.3 (d, 3J = 3.8, CH3); 73.2 (d,
2J = 5.7, CH); 115.4 (d, 1J = 286.2, C1); 126.9 (d,
0
0
0
0
32.2 (s, C4 ); 35.0 (s, C6 ); 40.9 (s, C8 ); 53.2 (s, C2 );
2
2
71.6 (d, J = 5.4, CH); 71.7 (d, J = 5.1, CH); 89.5 (s,
C1 ); 121.2 (d, J = 189.2, C1); 122.8 (d, J = 12.9, C5);
1
3
0
3
00
00
124.0 (d, J = 13.7, C3); 125.6 (s, C4 ); 126.3 (s, C2 );
2J = 14.6, C6); 127.7 (d, 3J = 6.3, C5); 133.7 (d, J = 2.5,
128.3 (s, C3 ); 132.2 (d, 4J = 2.4, C4); 133.5
4
00
C4); 133.9 (d, 3J = 8.8, C3); 141.8 (d, 2J = 8.8, C2).
(d, 2J = 8.8, C6); 150.1 (d, 2J = 10.3, C2); 151.2 (s,
C1 ). IR (KBr) cmꢀ1: 2975; 1448; 1243; 981; 759. MS
00
4.2.2. (ꢀ)-Menthyl 2-(diisopropylphosphoryl)benzenesulf-
enate 5. Yield 83%. Colourless oil. [a]D = ꢀ105 (c 1,
m/z (%): 527 (M+Na; 15); 313 (100); 271 (33); 229 (8).
HRMS calculated for C28H41O4PSNa (M+Na):
527.2361; found 527.2371.
1
3
CHCl3). H NMR (250 MHz): d 0.82 (d, 3H, JHH
=
3
6.9); 0.88 (d, 3H, JH3H = 7.0); 0.96 (d, 3H,
3JHH = 6.5); 1.23 (d, 6H, JHH = 6.1); 1.39 (d, 6H,
3JHH = 6.1); 0.80–1.08 (m, 2H); 1.20–1.47 (m, 3H);
4.2.5. (1R,2S)-trans-2-Phenyl-1-cyclohexyl 2-(diisoprop-
ylphosphoryl)benzenesulfenate 10. Yield 79%. Colourless

3412
M. Hamel et al. / Tetrahedron: Asymmetry 16 (2005) 3406–3415
1
oil. [a]D = ꢀ149.5 (c 1, CHCl3). H NMR (250 MHz): d
(%): 532 (M+; 28); 475 (11); 293 (73); 273 (75); 249
(16); 231 (32); 207 (35); 189 (100); 154 (12); 101 (14).
Analysis for C24H37O10PS: calculated (C: 54.12; H:
7.00); found: (C: 53.98; H: 7.49).
3
3
1.18 (d, 6H, JHH = 6.2); 1.35 (d, 6H, JHH = 6.2);
1.25–1.70 (m, 4H); 1.72–1.80 (m, 1H); 1.86–1.98 (m,
3
2H); 2.51–2.79 (m, 2H); 3.51 (dt, 1H, JHH = 10.1,
3
3
3JHH = 4.0); 4.63 (dsept, 2H, JHP = 7.5, JHH = 6.2);
3
4
6.30 (tt, 1H, JHH = 5.5, JHH = 0.9); 6.90–6.99 (m,
4.2.8. (2,4,6-Triisopropylphenyl)-2-(R)-ethyl 2-(diisoprop-
ylphosphoryl)benzenesulfenate 13. Yield 80%. Colour-
less oil. [a]D = +54.7 (c 0.85, CHCl3). 1H NMR
3
2H); 7.25–7.39 (m, 5H); 7.63 (ddd, 1H, JHH = 6.5,
3JHP = 14.0, JHH = 2.1). 31P NMR (100.1 MHz): d
4
16.5. 13C NMR (62.9 MHz): d 24.1 (d, J = 5.0, CH3);
(500 MHz): d 1.16 (d, 6H, JHH = 6.2); 1.20 (d, 6H,
3
3
3
3
24.4 (d, J = 3.8, CH3); 25.3 (s, C5 ); 26.2 (s, C4 ); 33.1
3JHH = 6.3); 1.25 (d, 6H, JHH = 7.0); 1.28 (d, 6H,
0
0
(s, C6 ); 33.7 (s, C3 ); 51.7 (s, C2 ); 71.4 (d, 2J = 5.0,
3JHH = 6.1); 1.33 (d, 6H, JHH = 6.2); 1.76 (d, 3H,
3
0
0
0
2
3
CH); 71.6 (d, J = 5.7, CH); 89.6 (s, C1 ); 121.5 (d,
J = 189.3, C1); 122.2 (d, J = 12.6, C5); 123.0 (s, C4 );
123.9 (d, J = 13.8, C3); 127.0 (s, C2 ); 128.7 (s, C3 );
3JHH = 6.8); 2.86 (sept, 1H, JHH = 6.9); 3.77–3.80 (m,
0
1
3
3
3
00
2H); 4.61 (dsept, 2H, JHP = 7.9, JHH = 7.1); 5.20
3
3
00
00
(qd, 1H, JHH = 6.9); 7.00 (s, 2H); 7.12 (dt, 1H,
4
2
4
3
132.5 (d, J = 2.5, C4); 133.6 (d, J = 8.2, C6); 144.2 (s,
3JHH = 7.6, JHP = 3.1); 7.42 (t, 1H, JHH = 7.2); 7.46–
C1 ); 148.2 (d, 2J = 10.1, C2). IR (NaCl) cmꢀ1: 2976;
7.49 (m, 1H); 7.73 (ddd, 1H, JHP = 14.1, JHH = 7.5,
3
3
00
1447; 1245; 980. MS m/z (%): 449 (MH+; 31); 407 (27);
365 (11); 291 (97); 273 (13); 249 (100); 231 (22); 207
(32); 159 (8). HRMS calculated for C24H34O4PS
(M+H): 449.1915; found 449.1914.
4JHH = 1.1). 31P NMR (202 MHz): d 16.6. 13C NMR
3
0
(126 MHz): d 22.9 (s, C8 ); 23.5 (d, J = 4.7, CH3(CH));
23.9 (d, J = 4.8, CH3(CH)); 23.9 (s, C10 ); 24.0 (s, C10 );
25.2 (s, C9 ); 29.2 (s, C1 ); 34.0 (s, C7 ); 71.1 (d, J = 5.4,
3
0
0
2
0
0
0
2
0
CH); 71.3 (d, J = 5.3, CH); 82.0 (s, C2 ); 120.9 (d,
3
1
0
4.2.6. (S)-Bornyl 2-(diisopropylphosphoryl)benzenesulfen-
ate 11. Yield 81%. Colourless oil. [a]D = ꢀ38.5 (c 0.74,
J = 12.9, C3); 121.3 (d, J = 191.4, C1); 123.3 (s, C5 );
3
0
123.7 (d, J = 13.7, C5); 132.2 (s, C3 ); 133.1 (s, C4);
1
2
0
0
CHCl3). H NMR (250 MHz): d 0.78 (s, 3H); 0.86 (s,
133.7 (d, J = 8.7, C6); 140.9 (s, C6 ); 148.0 (s, C4 );
3
2
3H); 1.02 (s, 3H); 1.23 (d, 6H, JHH = 6.2); 1.27–1.31
(m, 1H); 1.38 (d, 6H, JHH = 6.2); 1.64–1.78 (m, 4H);
148.5 (d, J = 10.6, C2). MS m/z (%): 521 (MH+; 5);
3
291 (16); 231 (100); 189 (7); 147 (4). IR (NaCl) cmꢀ1
:
2.05–2.11 (m, 1H); 2.24–2.31 (m, 1H); 3.91–3.97 (m,
1578; 1244; 986. HRMS calculated for C29H46O4PS
(M+H): 521.2854; found 521.2846.
3
3
1H); 4.66 (dsept, 2H, JHP = 11.8, JHH = 6.2); 7.14
4
3
4
(ddt, 1H, JHP = 8.3, JHH = 7.3, JHH = 1.4); 7.46–
3
3
7.59 (m, 2H); 7.76 (ddd, 1H, JHP = 14.1, JHH = 7.4,
4.3. Typical oxidation procedures of chiral sulfenates with
NBS in CH3CN–H2O
4JHH = 1.1). 31P NMR (101 MHz): d 16.3. 13C NMR
0
0
0
(62.9 MHz): d 14.4 (s, C7 ); 19.2 (s, C9 ); 20.2 (s, C9 );
24.1 (d, J = 5.0, CH3); 24.4 (d, 3J = 3.8, CH3); 26.7
NBS (208 mg, 1.17 mmol) was added portionwise to a
3
0
0
0
0
(s, C4 ); 28.5 (s, C5 ); 37.8 (s, C2 ); 45.3 (s, C3 ); 48.9 (s,
stirred solution of menthyl sulfenate 5 (500 mg,
2
0
0
0
C8 ); 50.7 (s, C6 ); 71.6 (d, J = 10.0, CH); 93.7 (s, C1 );
121.5 (d, 2J = 10.0, C6); 121.9 (d, 1J = 189.3, C1);
124.2 (d, 3J = 13.8, C3); 132.5 (d, 4J = 3.1,
C4); 134.1 (d, 3J = 8.8, C5); 148.9 (d, 2J = 10.1, C2).
IR (NaCl) cmꢀ1: 1579; 1244; 980. MS m/z (%): 427
(MH+; 67); 290 (100); 273 (23); 249 (32); 207 (83); 189
(64); 154 (9); 137 (40); 109 (8). HRMS calculated for
C22H36O4PS (M+H): 427.2072; found 427.2072.
1.17 mmol) in a mixture of acetonitrile and water 2/1.
The concentration of sulfenate ester was ca. 5 ·
10ꢀ2 M. After addition, stirring was continued for 5–
60 min and the mixture was quenched by adding a 5%
solution of H2SO4. The aqueous layer was extracted
three times with dichloromethane. The organic phase
was successively washed out with a 5% aqueous solution
of potassium carbonate and 5% sodium thiosulfate in
water. After drying and evaporation of the organic
solvent, the crude extract, whose purity was usually sat-
isfactory as shown by the NMR spectrum, was purified
on a silica gel column with pentane–ethyl acetate as elu-
ent to provide epimeric menthyl sulfinates 3a and 3b
(493 mg).
4.2.7. (Diacetone-D-glucosyl) 2-(diisopropylphosphoryl)-
benzenesulfenate 12. Yield 81%. Colourless oil. [a]D =
1
ꢀ139.1 (c 1, CHCl3). H NMR (500 MHz): d 1.20 (d,
3
3
6H, JHH = 6.2); 1.23 (d, 6H, JHH = 6.2); 1.27 (s,
3H); 1.36–1.38 (m, 6H); 1.43 (s, 3H); 3.98–4.03 (m,
1H); 4.07–4.11 (m, 1H); 4.15–4.19 (m, 2H); 4.47–4.53
3
3
(m, 1H); 4.66 (dsept, 2H, JHH = 6.2, JHP = 7.7); 4.88
With chiral Davis oxaziridines: A chiral oxaziridine
(69 mg, 0.23 mmol) was added portionwise to a stirred
solution of sulfenate ester 5 (100 mg, 0.23 mmol) in car-
bon tetrachloride (3–4 mL) under a nitrogen atmo-
sphere. After complete conversion, the solvent was
evaporated and the residue dissolved in pentane. The
mixture was filtered and washed once with pentane.
The sulfinate was further purified on silica gel chroma-
tography if necessary.
3
3
(d, 1H, JHH = 6.4); 5.89 (d, 1H, JHH = 3.7); 7.18 (dt,
3
4
3
1H, JHH = 7.2, JHP = 2.9); 7.47 (t, 1H, JHH = 7.3);
3
3
4
7.70 (ddd, 1H, JHH = 7.4, JHP = 13.7, JHH = 1.1);
7.86 (dd, 1H, JHH = 8.0, JHP = 5.7). 31P NMR (202
3
4
MHz): d 16.8. 13C NMR (125 MHz): d 23.6 (d,
3J = 4.8, CH3); 24.0 (d, J = 4.9, CH3); 25.5 (s, C8 );
3
0
0
0
0
0
26.1 (s, C8 ); 26.6 (s, C10 ); 26.9 (s, C10 ); 67.8 (s, C5 );
71.4 (d, J = 5.0, CH); 71.5 (d, J = 5.4, CH); 71.7 (s,
2
2
0
0
0
0
C5 ); 81.4 (s, C4 ); 83.2 (s, C1 ); 86.1 (s, C2 ); 104.8 (s,
3
0
0
0
C3 ); 109.3 (s, C7 ); 111.9 (s, C9 ); 121.8 (d, J = 12.5,
With mCPBA: Sulfenate ester 5 (200 mg, 0.47 mmol)
was oxidized by the addition of 108 mg (0.47 mmol,
75% purity) of mCPBA in CH2Cl2 or THF at ꢀ78 ꢁC.
The reaction was allowed to reach room temperature.
1
3
C3); 122.0 (d, J = 189.3, C1); 124.5 (d, J = 12.5, C5);
132.3 (s, C4); 133.3 (d, 2J = 8.4, C6); 146.3 (d,
2J = 10.3, C2). IR (NaCl) cmꢀ1: 1217; 986. MS m/z

M. Hamel et al. / Tetrahedron: Asymmetry 16 (2005) 3406–3415
3413
3
3
The solvent was evaporated and the crude sulfinate
directly purified by silica gel chromatography.
3JHH = 4.4); 4.80 (dsept, 2H, JHP = 8.5, JHH = 6.7);
3
4
6.97 (tt, 1H, JHH = 7.0, JHH = 1.4); 7.04–7.13 (m,
2H); 7.22–7.31 (m, 2H); 7.52–7.58 (m, 1H); 7.60–7.67
3
3
4.3.1. (ꢀ)-Menthyl 2-(diisopropylphosphoryl)benzene-
sulfinate 3. Yield 95%. Colourless oil. [a]D = +10.0
(c 1, CHCl3); dr: 12/88. NMR of the major diastereo-
(m, 2H); 7.87 (ddd, 1H, JHH = 7.6, JHP = 3.7,
4JHH = 1.3); 8.00–8.04 (m, 1H). 31P (162 MHz): d
C (100.6 MHz): d 22.2 (s, C7 ); 24.1 (d,
J = 4.7, CH3); 24.4 (s, C9 ); 24.6 (d, J = 4.3, CH3);
13
0
13.18.
1
3
3
3
0
mer: H (250 MHz): d 0.71 (d, 3H, JHH = 6.9); 0.82
3
3
0 0 0 0
25.1 (s, C9 ); 27.6 (s, C3 ); 28.7 (s, C5 ); 32.2 (s, C4 );
(d, 3H, JHH = 7.0); 0.90 (d, 3H, JHH = 6.3); 1.23 (d,
3
3
0
0
0
3H, JHH = 6.0); 1.26 (d, 3H, JHH = 6.0); 1.39 (d, 3H,
34.8 (s, C6 ); 40.5 (s, C8 ); 52.5 (s, C2 ); 72.0 (d,
3JHH = 6.2); 1.42 (d, 3H, JHH = 6.2); 0.80–1.43
2J = 6.3, CH); 72.3 (d, J = 5.9, CH); 83.3 (s, C1 );
3
2
0
00
00
00
(m, 4H); 1.61–1.67 (m, 2H); 1.90–2.10 (m, 3H); 4.22
124.7 (s, C2 ); 125.2 (s, C4 ); 125.7 (s, C3 ); 126.1
3
3
(dt, 1H, JHH = 10.7, JHH4 = 4.5); 4.67–4.90 (m, 2H);
(d, 3J = 7.8, C3); 127.1 (d, 1J = 197.0, C1); 128.4 (d,
3
4
7.57 (ddt, 1H, JHH = 7.7, JHH = 1.2, JHP = 3.2); 7.74
2J = 14.0, C6); 131.2 (d, 2J = 14.1, C2); 132.9 (d,
3
3
4
3J = 8.0, C5); 133.7 (d, J = 3.0, C4); 151.6 (s, C1 ).
00
(tt, 1H, JHH = 7.7); 7.92 (ddd, 1H, JHH = 7.7,
4JHH = 1.2, JHP = 13.6); 8.24 (ddd, 1H, JHH = 7.7,
Minor diastereomer: 1H (400 MHz): d 0.91 (d, 3H,
3JHH = 5.7); 2.43–2.46 (m, 1H); 4.30–4.36 (m, 1H);
4.67–4.81 (m, 2H); 7.74–7.79 (m, 1H); 7.87–7.95 (m,
1H). 31P (162 MHz): d 13.39. 13C (100.6 MHz): d 22.3
3
3
4JHH = 1.2, JHP = 4.9). 31P (101.2 MHz): d 13.95. 13C
4
0
0
0
(62.9 MHz): d 16.3 (s, C9 ); 21.3 (s, C9 ); 22.7 (s, C9 );
3
3
0
23.7 (s, C3 ); 24.1 (d, J = 4.9, CH3); 24.2 (d, J = 4.9,
3
3
0 0 0 0
(s, C7 ); 25.9 (s, C9 ); 27.7 (s, C3 ); 28.3 (s, C5 ); 30.0 (s,
CH3); 24.4 (d, J = 3.9, CH3); 24.5 (d, J = 3.9, CH3);
0
0
0
0
0 0 0 0
C4 ); 34.9 (s, C6 ); 40.6 (s, C8 ); 51.6 (s, C2 ); 80.1 (s,
25.7 (s, C8 ); 32.2 (s, C4 ); 34.4 (s, C5 ); 43.4 (s, C6 );
2
2
0
0 00 00 00
48.6 (s, C2 ); 72.0 (d, J = 6.0, CH); 72.2 (d, J = 5.8,
C1 ); 124.8 (s, C2 ); 125.3 (s, C4 ); 125.4 (s, C3 ); 127.8
CH); 80.4 (s, C1 ); 124.7 (d, 3J = 11.9, C3); 128.0 (d,
(d, J = 187.0, C1); 131.3 (d, J = 13.1, C2); 133.4 (d,
1
2
0
1J = 188.7, C1); 131.4 (d, 3J = 13.2, C5); 133.3 (d,
J = 8.0, C5); 133.6 (d, J = 3.0, C4); 150.5 (s, C1 ). IR
3
4
00
2J = 12.0, C6); 133.4 (d, J = 3.1, C4); 149.5 (d, 2J =
(NaCl) cmꢀ1: 2975; 1454; 1247; 1121 (R–SO–OR0);
983; 732 (S–O st). MS m/z (%): 543 (M+Na; 31); 329
(100); 288 (28); 245 (8). HRMS calculated for
C28H41O5NaPS (M+Na): 543.2310; found 543.2282.
4
1
10.0, C2). Minor diastereomer: H (250 MHz): d 4.10–
4.20 (m, 1H); 4.42–4.59 (m, 2H). 31P (101.2 MHz): d
13
0
14.13. C (62.9 MHz): d 79.5 (s, C1 ). IR (NaCl)
cmꢀ1: 2954; 2869; 1582; 1454; 1386; 1374; 1255 (mP@O);
1178; 1128 (mS@O); 1103; 982 (mP–O); 757 (mS–O). MS
m/z (%): 445 (MH+; 31); 307 (21); 289 (12); 247 (20);
206 (20); 205 (100); 159 (10). HRMS calculated for
C22H38O5PS (M+H): 445.2178 found: 445.2173.
4.3.4. ((1R,2S)-trans-2-Phenyl-1-cyclohexyl) 2-(diisoprop-
ylphosphoryl)benzenesulfinate 15. Yield 67%. Colour-
less oil. [a]D = ꢀ56.9 (c 2.9, CHCl3); dr: 87/13. NMR
1
of the major diastereomer (CD3OD): H (400 MHz): d
3
3
1.22 (d, 3H, JHH = 6.2); 1.23 (d, 3H, JHH = 6.1);
3
3
4.3.2. Methyl 2-(diisopropylphosphoryl)benzenesulfinate
1.34 (d, 3H, JHH = 6.2); 1.35 (d, 3H, JHH = 6.4);
8. Yield 66%. Colourless liquid. ee: 20%. 1H NMR
1.30–1.89 (m, 7H); 2.20–2.25 (m, 1H); 2.69–2.74 (m,
3
3
3
(250 MHz): d 1.25 (d, 3H, JHH = 6.2); 1.26 (d, 3H,
1H); 4.48 (dt, 1H, JHH = 10.5, JHH = 6.2); 4.60–4.75
3JHH = 6.2); 1.40 (d, 3H, JHH = 6.0); 1.42 (d, 3H,
(m, 2H); 6.99–7.11 (m, 5H); 7.54–7.61 (m, 2H); 7.75–
3
3JHH = 6.0); 3.73 (s, 3H); 4.73–4.80 (m, 2H); 7.62 (ddt,
7.81 (m, 2H). 31P (161 MHz):
d
13.04. 13C
3
4
4
1H, JHH = 7.5, JHH = 1.3, JHP = 3.0); 7.76 (tt, 1H,
(100.6 MHz): d 23.1 (d, 3J = 4.6, CH3); 23.2 (d,
3JHH = 7.5, JHH = 5JHP = 1.5); 7.95 (ddd, 1H, JHH
=
=
3J = 4.6, CH3); 23.3 (d, 3J = 3.9, CH3); 23.4 (d,
4
3
4
3
3
3
0
0
0
7.5, JHH = 1.5, JHP = 13.7); 8.22 (ddd, 1H, JHH
J = 4.3, CH3); 24.9 (s, C5 ); 25.6 (s, C4 ); 34.1 (s, C3 );
7.5, JHH = 1.3, JHP = 4.8). 31P NMR (101.2 MHz): d
34.2 (s, C6 ); 51.1 (s, C2 ); 72.7 (d, J = 6.1, CH); 73.0
(d, J = 5.8, CH); 82.5 (s, C1 ); 124.4 (d, J = 12.6, C3);
4
4
2
0
0
13.8. 13C NMR (62.9 MHz): d 24.1 (d, J = 4.8, CH3);
3
2
3
0
3
3
1
00
00
24.2 (d, J = 4.8, CH3); 24.3 (d, J = 4.0, CH3); 24.4
(d, J = 4.2, CH3); 53.7(s, CH3–O); 72.0 (d, J = 5.7,
126.4 (s, C4 ); 127.1 (d, J = 190.3, C1); 127.8 (s, C3 );
128.2 (s, C2 ); 131.5 (d, 3J = 13.4, C5); 132.8 (d,
3
2
00
2
3
4
2J = 8.5, C6); 133.7 (d, J = 2.9, C4); 143.0 (s, C1 );
00
CH); 72.1 (d, J = 5.7, CH); 124.7 (d, J = 12.3, C5);
128.8 (d, 1J = 189.0, C1); 131.8 (d, 3J = 13.1, C3);
132.9 (d, 4J = 3.0, C4); 134.1 (d, 2J = 8.3, C6); 147.9
2
151.2 (d, J = 10.5, C2). Minor diastereomer (CD3OD):
1H (400 MHz): d 2.35–2.41 (m, 1H); 2.67–2.72 (m, 1H);
7.18–7.29 (m, 5H); 7.48–7.54 (m, 2H); 7.81–7.87 (m,
2H). 31P (161 MHz): d 12.95. 13C (100.6 MHz): d 24.8
(d, J = 10.5, C2). IR (NaCl) cmꢀ1: 3480; 2979; 2936;
2
1582; 1454; 1428; 1386; 1375; 1255 (mP@O); 1178; 1130
(mS@O); 1103; 984 (mP–O); 769 (mS–O). GC/MS m/z
(%): 321 (MH+; 7); 289 (29); 219 (11); 206 (14); 205
(100); 188 (8); 139 (14). HRMS calculated for
C13H22O5PS (M+H): 321.0926; found 321.0931.
0
0
0
0
(s, C5 ); 25.7 (s, C4 ); 33.4 (s, C3 ); 34.5 (s, C6 ); 80.5 (s,
C1 ); 125.0 (d, J = 12.4, C3); 128.0 (s, C3 ); 128.3 (s,
C2 ); 131.7 (d, J = 13.6, C5); 132.6 (d, J = 9.3, C6);
3
0
00
3
2
00
2
00
133.7 (s, C4); 143.3 (s, C1 ); 151.6 (d, J = 10.4, C2).
IR (NaCl) cmꢀ1: 2979; 2931; 1248 (P@O); 1124
(S@O); 988 (P–O–C). MS m/z (%): 487 (M+Na; 43);
445 (10); 329 (76); 313 (51); 287 (100); 271 (28); 245
(46); 227 (29). HRMS calculated for C24H34O5PS
(M+H): 465.1865; found 465.1856.
4.3.3. L-(8-Phenyl)-menthyl 2-(diisopropylphosphoryl)-
benzenesulfinate 14. Yield 70%. Colourless oil.
[a]D = ꢀ15.2 (c 0.7, CHCl3); dr: 17.5/82.5. NMR of
the major diastereomer: 1H (400 MHz): d 0.72–1.05
(m, 2H); 0.89 (d, 3H, JHH = 5.8); 1.11 (s, 3H); 1.19 (s,
3H); 1.20–1.56 (m, 4H); 1.27 (d, 6H, JHH = 6.4); 1.29
3
3
4.3.5. (S)-Bornyl 2-(diisopropylphosphoryl)benzenesulfi-
nate 16. Yield 92%. Colourless oil. [a]D = +3.0 (c 0.75,
CHCl3); dr: 62/38. NMR of the major diastereomer:
3
(d, 6H, JHH = 6.4); 1.91–1.98 (m, 1H); 1.91–1.98 (m,
1H); 2.35–2.41 (m, 1H); 4.49 (dt, 1H, JHH = 10.5,
3

3414
M. Hamel et al. / Tetrahedron: Asymmetry 16 (2005) 3406–3415
1H (250 MHz): d 0.76 (s, 3H); 0.78 (s, 3H); 0.78–0.81
less oil. [a]D = +47.0 (c 1.35, CHCl3); dr: 7/93. NMR
of the major diastereomer: H (400 MHz): d 0.89 (d,
3
1
(m, 3H); 0.93–1.00 (m, 1H); 1.15 (d, 6H, JHH = 6.2);
3
3
3
1.20 (d, 6H, JHH = 6.2); 1.26–1.20 (m, 1H); 1.33 (d,
3H, JHH = 6.2); 0.96 (d, 3H, JHH = 6.1); 1.10 (d, 3H,
3JHH = 6.2); 1.15–1.25 (m, 21H); 1.80 (d, 3H,
3
3
6H, JHH = 6.2); 1.34 (d, 6H, JHH = 6.0); 1.64–1.78
3
(m, 4H); 2.20–2.31 (m, 1H); 4.51–4.83 (m, 3H); 7.51
3JHH = 6.9); 2.80 (sept, 1H, JHH = 6.9); 3.25–3.36 (m,
3
4
4
3
(ddt, 1H, JHH = 7.4, JHP = 3.1, JHH = 1.1); 7.63–
1H); 3.50–3.62 (m, 1H); 4.40 (dsept, 1H, JHP = 7.9,
3
3
3
3
7.71 (m, 1H); 7.90 (ddd, 1H, JHP = 13.4, JHH = 7.5,
3JHH = 6.2); 4.58 (dsept, 1H, JHP = 10.4, JHH = 6.3);
4JHH = 1.2); 8.14–8.24 (m, 1H). 31P (162 MHz): d
6.11 (qd, 1H, JHH = 6.8); 6.93 (s, 2H); 7.46–7.49 (m,
3
13
3
0
0
13.06. C (62.9 MHz): d 12.2 (s, C7 ); 17.8 (s, C9 );
18.7 (s, C9 ); 22.7 (d, J = 4.8, CH3); 23.0 (d, J = 4.9,
1H); 7.75 (t, 1H, JHH = 6.5); 7.87 (ddd, 1H,
3
3
3
4
3JHP = 14.8, JHH = 7.5, JHH = 1.2); 8.31 (ddd, 1H,
0
CH3); 25.7 (s, C4 ); 26.9 (s, C5 ); 35.4 (s, C2 ); 43.9 (s,
3JHH = 7.9, JHP = 4.8, JHH = 1.0). 31P (161 MHz): d
4
4
0
0
0
2
3
C3 ); 46.6 (s, C8 ); 48.7 (s, C6 ); 70.8 (d, J = 6.2, CH);
12.90. 13C (62.9 MHz): d 23.4 (d, J = 4.9, CH3(CH));
0
0
0
81.2 (s, C1 ); 123.1 (d, 2J = 12.5, C6); 127.1 (d, 1J =
23.5 (d, 3J = 4.9, CH3(CH)); 23.7 (d, 3J = 4.0,
0
3
3
0
189.3, C1); 130.1 (d, JCP = 13.3, C3); 131.9 (s, C4);
CH3(CH)); 23.9 (d, J = 4.1, CH3(CH)); 24.3 (s, C8 );
132.4 (d, 3J = 9.4, C5); 149.4 (d, 2J = 8.6, C2). Minor dia-
24.4 (s, C10 ); 24.7 (s, C9 ); 29.3 (s, C1 ); 34.1 (s, C7 );
0
0
0
0
stereomer: 1H (250 MHz): d 0.92–0.99 (m, 6H); 4.51–4.83
71.5 (d, J = 6.3, CH); 71.6 (d, J = 6.3, CH); 74.8 (s,
0 0 0
C2 ); 120.7 (s, C5 ); 123.2 (s, C3 ); 124.3 (d, J = 11.9,
C3); 127.7 (d, J = 188.0, C1); 131.0 (d, J = 13.2, C5);
132.9 (d, J = 2.5, C4); 133.1 (d, J = 7.5, C6); 145.1 (s,
2
2
(m, 3H); 7.81–7.90 (m, 1H). 31P (162 MHz): d 12.99. 13
C
3
1
3
0
0
0
(62.9 MHz): d 12.0 (s, C7 ); 18.9 (s, C9 ); 35.9 (s, C2 ); 43.8
4
2
0
0
0
(s, C3 ); 47.2 (s, C8 ); 84.9 (s, C1 ); 123.3 (s, C6); 132.2 (s,
C4); 149.6 (s, C2). IR (NaCl) cmꢀ1: 2979; 1247; 1106
(S@O); 992; 909; 735. HRMS for C22H36O5PS (M+H):
calculated 443.2013; found 443.2012.
2
0
0
C6 ); 148.0 (s, C4 ); 151.1 (d, J = 10.1, C2). Minor dia-
1
stereomer: H (400 MHz): d 4.70–4.82 (m, 1H); 8.20–
8.24 (m, 1H). 31P (161 MHz): d 13.09. IR (NaCl)
cmꢀ1: 2963; 2871; 2239; 1460; 1378; 1249; 1125; 986.
MS m/z (%): 559 (M+Na; 18); 330 (21); 329 (100); 287
(16). HRMS calculated for C29H46O5PS (M+H):
537.2804; found 537.2794.
4.3.6. (Diacetone-D-glucosyl) 2-(diisopropylphosphoryl)-
benzenesulfinate 17. Yield 94%. Colourless oil. [a]D =
+13.6 (c 1.88, CHCl3); dr: 32/68. NMR of the major
diastereomer: 1H (400 MHz): d 1.22–1.51 (m, 24H); 3.50
2
3
(dd, 1H, JHH = 8.5, JHH = 6.6); 3.82 (dd, 1H,
2JHH = 8.5, 3JHH = 6.4); 4.27–4.33 (m, 1H); 4.44 (d, 1H,
JHH = 4.2); 4.65 (d, 1H, JHH = 3.7); 4.77–4.91 (m, 2H);
4.98 (d, 1H, JHH = 3.0); 5.92 (d, 1H, JHH = 3.7); 7.62–
7.69 (m, 1H); 7.75–7.80 (m, 1H); 7.92 (dd, 1H,
4.4. The Grignard reaction leading to diisopropyl
(2-methylsulfinyl)phenylphosphonate 6
Menthyl sulfinate ester 5 (500 mg, 1.12 mmol) was
added dropwise at 0 ꢁC to a solution of methylmagne-
sium bromide (3 M in Et2O, 1.12 mL, 3.36 mmol) in
diethyl ether. The mixture was stirred for 1 h at room
temperature. A 5% aqueous solution of sulfuric acid
(10 mL) was added and the aqueous layer extracted with
diethyl ether. The organic extracts were washed succes-
sively with a 5% aqueous solution of potassium carbon-
ate and brine, dried over MgSO4, filtered and
evaporated to afford a yellow oil, which was further
purified on silica gel chromatography.
3
3
3JHP = 13.7, JHH = 7.5); 8.24 (dd, 1H, JHH = 7.3,
4JHP = 4.6). 31P (101 MHz): d 12.05. 13C (62.9 MHz): d
3
3
22.7 (d, J = 4.7, CH3); 22.8 (d, J = 4.4, CH3); 23.0 (d,
3J = 4.3, CH3); 23.1 (d, J = 4.1, CH3); 24.3 (s, C8 );
3
0
0
0
0
0
25.2 (s, C8 ); 25.4 (s, C10 ); 25.7 (s, C10 ); 64.3 (s, C6 );
2
2
71.0 (d, J = 6.1, CH); 71.2 (d, J = 6.0, CH); 72.1 (s,
0
0
0
0
C5 ); 79.2 (s, C4 ); 80.0 (s, C1 ); 82.5 (s, C2 ); 104.0 (s,
3
0
0
0
C3 ); 107.3 (s, C7 ); 111.1 (s, C9 ); 122.7 (d, J = 12.6,
1
3
C3); 126.9 (d, J = 189.3, C1); 130.9 (d, J = 11.9, C5);
132.1 (s, C4); 132.2 (d, 2J = 6.9, C6); 148.6 (d, 2J = 10.7,
C2). Minor diastereomer: 1H (400 MHz): d 3.91–3.94
(m, 1H); 4.90 (d, 1H, JHH = 3.7); 5.86 (d, 1H,
The reaction was extended to sulfinates derived from 8-
phenylmenthol 14, trans-2-phenylcyclohexanol 15 and
GreeneÕs alcohol 18 (Table 2, entries 2, 4 and 13, respec-
tively). The 2-phosphorylated phenyl methyl sulfoxide
(R)-(+)-6 was formed in 85% and 74% ee in the two for-
mer cases, while the (S)-(ꢀ)-6 isomer was produced in
the latter with 86% ee.
JHH = 3.6); 8.27–8.29 (m, 1H). 31P (101 MHz): d 12.23.
13
0
0
C (62.9 MHz): d 24.1 (s, C8 ); 25.6 (s, C8 ); 25.8 (s,
C10 ); 25.9 (s, C10 ); 65.7 (s, C6 ); 70.8 (d, J = 5.7, CH);
2
0
0
0
0
0
0
0
71.6 (s, C5 ); 78.7 (s, C4 ); 79.3 (s, C1 ); 82.2 (s, C2 );
0
0
0
104.1 (s, C3 ); 107.8 (s, C7 ); 111.1 (s, C9 ); 122.7 (d,
3J = 12.7, C3); 127.2 (d, 1J = 188.7, C1); 130.6 (d,
3J = 13.2, C5); 148.5 (d, 2J = 10.7, C2). IR (NaCl) cmꢀ1
:
Yield 78%. Colourless liquid. [a]D = ꢀ145.2 (c 1.3,
CHCl3). Ee = 86%. 1H NMR (400 MHz): d 1.27 (d,
2983; 2936; 2249; 1735; 1455; 1376; 1248; 1138; 989;
732. MS m/z (%): 571 (M+Na; 35); 529 (12); 313 (100);
271 (37); 269 (16); 227 (13). HRMS for C29H38O10PS
(M+H): calculated 549.1923; found 549.1944.
3
3
3H, JHH = 7.1); 1.29 (d, 3H, JHH = 6.6); 1.37 (d, 3H,
3JHH = 6.2); 1.43 (d, 3H, JHH = 6.2); 2.87 (s, 3H);
3
3
3
4.77 (dsept, 2H, JHH = 6.2, JHP = 7.9); 7.57 (ddt,
3
3
4
1H, JHH = 7.3, JHP = 3.0, JHH = 0.8); 7.79 (t, 1H,
3
3
The DAG-sulfinates 17 (94 mg) were recrystallized twice
from a mixture of ether–pentane 2:1 to give diastereo-
merically pure 17b (43 mg, 46%) according to 31P
NMR: dP 12.11 (100%). [a]D = +102.3 (c 0.3, CHCl3).
3JHH = 7.7); 7.86 (ddd, 1H, JHH = 7.5, JHP = 13.5,
4JHH = 0.8); 8.29 (dd, 1H, JHH = 7.6, JHP = 5.6). 31P
3
4
NMR (162 MHz): d 12.7. 13C NMR (100 MHz): d
3
3
24.2 (d, J = 4.8, CH); 24.3 (d, J = 4.9, CH); 24.4 (d,
3J = 3.8, CH); 24.5 (d, 3J = 4.1, CH); 45.2 (s, CH3(SO));
72.3 (d, 2J = 6.0, CH); 124.1 (d, 3J = 12.5, C3); 127.4 (d,
1J = 190.1, C1); 130.7 (d, 2J = 13.1, C6); 133.3 (d,
4.3.7. (2,4,6-Triisopropylphenyl)-2-(R)-ethyl 2-(diisoprop-
ylphosphoryl)benzenesulfinate 18. Yield 85%. Colour-

M. Hamel et al. / Tetrahedron: Asymmetry 16 (2005) 3406–3415
3415
3J = 8.1, C5); 133.8 (d, 4J = 2.9, C4); 151.1 (d, 2J = 10.9,
C2). IR (NaCl) cmꢀ1: 2978; 2933; 1581; 1454; 1426; 1386;
1375; 1251 (mP@O); 1178; 1141; 1103; 1066 (mS@O); 984
(mP–O); 769 (mS–O). GC/MS m/z (%): 305 (MH+; 5); 205
(100); 204 (18); 203 (19); 206 (95); 159 (17); 139 (13).
Analysis for C13H21O4PS: calculated (C: 51.31; H: 6.96;
S: 10.53) found (C: 51.42; H: 7.05; S: 10.25).
7. (a) Hiroi, K.; Suzuki, Y.; Kawagishi, R. Tetrahedron Lett.
1999, 40, 715–718; (b) Hiroi, K.; Suzuki, Y.; Abe, I.;
Kawagishi, R. Tetrahedron 2000, 56, 4701–4710.
8. (a) Masson, S.; Saint-Clair, J.-F.; Saquet, M. Synthesis
1993, 485–486; (b) Masson, S.; Saint-Clair, J.-F.; Saquet,
M. Tetrahedron Lett. 1994, 35, 3083–3084; (c) Masson, S.;
Saint-Clair, J.-F.; Dore, A.; Saquet, M. Bull. Soc. Chim.
Fr. 1996, 133, 951–964.
9. Mauger, C.; Vazeux, M.; Masson, S. Tetrahedron Lett.
2004, 45, 3855–3859.
10. (a) Drabowicz, J.; Kielbasinski, P.; Mikolajczyk, M. In
The syntheses of sulphones, sulphoxides and cyclic sulp-
hides; Patai, S., Rappoport, Z., Eds.; John Wiley & Sons,
1988; pp 109–387; (b) Fernandez, I.; Khiar, N. Chem. Rev.
Acknowledgements
This workwas carried out with the support of the
European Community within the fifth framework
programme (contract ICA-CT-2000-70021-Centre of
Excellence) of the French CNRS (Centre National de
la Recherche Scientifique) and the Polish Academy of
Sciences. We gratefully acknowledge the ÔMinistere de
la Recherche et des Nouvelles TechnologiesÕ for the
2003, 103, 3651–3705; (c) Carreno, M. C. Chem. Rev.
˜
1995, 95, 1717–1760; (d) Madesclaire, M. Tetrahedron
1986, 42, 5459–5495; (e) Kagan, H. B. In Catalytic
Asymmetric Synthesis, 2nd ed.; Ojima, L., Ed.; Wiley-
VCR: New York, 2000, Chapter 6c; (f) Mikolajczyk, M.;
Drabowicz, J.; Kielbasinski, P. In ÔChiral Sulfur ReagentsÕ
Applications in Asymmetric and Stereoselective Synthesis;
CRC Press, 1997.
`
´
Grant to M.H. and the ÔRegion Basse-NormandieÕ and
the European Union (FEDER funding), for financial
support. Authors thankwarmfully Prof. Andrew
Greene for his generous gift of samples of the (R)-(ꢀ)-
(2,4,6-triisopropylphenyl)ethanol.
11. Mauger, C.; Masson, S.; Vazeux, M.; Saint-Clair, J.-F.;
Midura, W. H.; Drabowicz, J.; Mikolajczyk, M. Tetra-
hedron: Asymmetry 2001, 12, 167–174.
12. Mauger, C. Ph.D. Dissertation, Caen University, 2000.
13. (a) Phillips, H. J. Chem. Soc. 1925, 127, 2552–2587; (b)
Andersen, K. K. Tetrahedron Lett. 1962, 3, 93–95; (c)
Andersen, K. K.; Gaffield, W.; Papanikolaou, N. E.;
Foley, J. W.; Perkins, R. I. J. Am. Chem. Soc. 1964, 86,
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