Reactivities of novel [hydroxy(tosyloxy)iodo]arenes and [hydroxy(phosphoryloxy)iodo]arenes for α-tosyloxylation and α-phosphoryloxylation of ketones

Article abstract of DOI:10.1021/jo0200670

Novel [hydroxy(tosyloxy)iodo]arenes bearing 2-thienyl, 3-thienyl, N-tosyl-4-pyrazolyl, 3-trifluoromethylphenyl, and 3,5-bis(trifiuoromethy)phenyl as an aromatic group, and [hydroxy(phosphoryloxy)iodo]arenes bearing N. tosyl-4-pyrazolyl, 3-trifluoromethylp

Full text of DOI:10.1021/jo0200670

4362
J . Org. Chem. 2002, 67, 4362-4365
Notes
Rea ctivities of Novel
[Hyd r oxy(tosyloxy)iod o]a r en es a n d
[Hyd r oxy(p h osp h or yloxy)iod o]a r en es for
r-Tosyloxyla tion a n d
r-P h osp h or yloxyla tion of Keton es
Takahiro Nabana† and Hideo Togo*,†,‡
Graduate School of Science and Technology, and
Department of Chemistry, Faculty of Science, Chiba
University, Yayoi-cho 1-33, Inage-ku, Chiba 263-8522 J apan
togo@scichem.s.chiba-u.ac.jp
Received J anuary 29, 2002
Ab st r a ct : Novel [hydroxy(tosyloxy)iodo]arenes bearing
2-thienyl, 3-thienyl, N-tosyl-4-pyrazolyl, 3-trifluorometh-
ylphenyl, and 3,5-bis(trifluoromethy)phenyl as an aromatic
group, and [hydroxy(phosphoryloxy)iodo]arenes bearing N-
tosyl-4-pyrazolyl, 3-trifluoromethylphenyl, and 3,5-bis(tri-
fluoromethy)phenyl as an aromatic group, were prepared.
R-Tosyloxylation and R-phosphoryloxylation of ketones with
these compounds were carried out, respectively. Their re-
activities were compared with that of the parent [hydroxy-
(tosyloxy)iodo]benzene and [hydroxy(phosphoryloxy)iodo]-
benzene, respectively, and consequently [hydroxy(tosyloxy)-
iodo]arenes and [hydroxy(phosphoryloxy)iodo]arenes bearing
3-trifluoromethylphenyl and 3,5-bis(trifluoromethy)phenyl
as an aromatic group showed the best reactivity. These new
compounds can be used as powerful R-tosyloxylation and
R-phosphoryloxylation reagents, instead of the parent [hy-
droxy(tosyloxy)iodo]benzene and [hydroxy(phosphoryloxy)-
iodo]benzene.
F igu r e 1. Novel [hydroxy(tosyloxy)iodo]arenes and [hydroxy-
(phosphoryloxy)iodo]arenes.
iodonium tosylate.2 However, to our knowledge, detailed
study on the preparation of [hydroxy(tosyloxy)iodo]arenes
bearing other aromatics instead of a phenyl group and
their synthetic uses have been rather limited.3 Thus, we
planned to prepare novel [hydroxy(tosyloxy)iodo]arenes
and [hydroxy(phosphoryloxy)iodo]arenes and compare
their reactivities for R-tosyloxylation and R-phosphory-
loxylation4 of ketones with those of [hydroxy(tosyloxy)-
iodo]benzene and [hydroxy(phosphoryloxy)iodo]benzene,
respectively. Two types of aromatics, π-excess aromatics
(thienyl) and π-deficient aromatics (pyrazolyl, trifluo-
romethylphenyl, and bis(trifluoromethyl)phenyl), i.e.,
2-thienyl (2), 3-thienyl (3), N-tosyl-4-pyrazolyl (4), 3-tri-
fluoromethylphenyl (5), and 3,5-bis(trifluoromethy)phen-
yl (6), were prepared by treatment of the corresponding
iodoarenes with sodium perborate or peracetic acid in
acetic acid, and subsequent treatment with p-toluene-
sulfonic acid or diphenylphosphoric acid as shown in
Figure 1. The conversion of (diacetoxyiodo)arenes to
[hydroxy(tosyloxy)iodo]arenes in acetonitrile proceeded
smoothly to give compounds 2A-6A in quite good yields.
At first, the R-tosyloxylation of acetophenone with
compounds 2A-6A was carried out under the same
Recently, extensive study on hypervalent iodine com-
pounds such as (diacetoxyiodo)benzene, [bis(trifluoro-
acetoxy)iodo]benzene, [hydroxy(tosyloxy)iodo]benzene, etc.,
has been carried out and their use for organic synthesis
has been reported.1 Among them, [hydroxy(tosyloxy)iodo]-
benzene (Koser’s reagent) is a useful reagent for R-tosyl-
oxylation of ketones which are the precursors for the
construction of heterocyclic compounds such as thiazoles,
selenazoles, oxazoles, imidazoles, pyrazoles, benzofurans,
and lactones, and for the formation of alkynyl phenyl
(2) (a) Koser, G. F.; Wettach, R. H.; Troup, J . M.; Frenz, B. A. J .
Org. Chem. 1976, 41, 3609. (b) Koser, G. F.; Wettach, R. H. J . Org.
Chem. 1977, 42, 1476. (c) Koser, G. F.; Relenyi, A. G.; Kalos, A. N.;
Rebrovic, L.; Wettach, R. H. J . Org. Chem. 1982, 47, 2487. (d) Moriarty,
R. M.; Penmasta, R.; Awasthi, A. K.; Epa, W. R.; Prakash, I. J . Org.
Chem. 1989, 54, 1101. (e) Moriarty, R. M.; Vaid, R. K.; Hopkins, T. E.;
Vaid, B. K.; Prakash, O. Tetrahedron Lett. 1990, 31, 201. (f) Moriarty,
R. M.; Vaid, B. K.; Duncan, M. P.; Levy, S. G.; Prakash, O.; Goyal, S.
Synthesis 1992, 845. (g) Tuncay, A.; Dustman, J . A.; Fisher, G.; Tuncay,
C. I. Tetrahedron Lett. 1992, 33, 7647. (h) Prakash, O.; Goyal, S.
Synthesis 1992, 629. (i) Prakash, O.; Saini, N.; Sharma, P. K. Synlett
1994, 221. (j) Prakash, O.; Saini, N.; Sharma, P. K. Heterocycles 1994,
38, 409. (k) Lee, J . C.; Choi, J u-H. Synlett 2001, 234.
(3) Ligand exchange reaction of [hydroxy(tosyloxy)iodo]benzene with
p-iodoarenes (Cl, Br, I, CH3, NO2, Ph) to form para-substituted
[hydroxy(tosyloxy)iodo]benzene: Koser, G. F.; Wettach, R. H.; Smith,
C. S. J . Org. Chem. 1980, 45, 1544. Preparation of [hydroxy(tosyloxy)-
iodo]pentafluorobenzene and formation of iodonium species: Moriarty,
R. M.; Penmasta, R.; Prakash, I. Tetrahedron Lett. 1987, 28, 877.
(4) Koser, G. F.; Lodaya, J . S.; Ray, D. G., III; Kokil, P. B. J . Am.
Chem. Soc. 1988, 110, 2987.
† Graduate School of Science and Technology.
‡ Department of Chemistry.
(1) Varvoglis A. Hypervalent Iodine in Organic Synthesis; Academic
Press: San Diego 1997. Recent reviews: (b) Ochiai, M. Rev. Heteroatom
Chem. 1989, 2, 92. (c) Moriarty, R. M.; Vaid, R. K.; Koser, G. F. Synlett
1990, 365. (d) Moriarty, R. M.; Vaid, R. K. Synthesis 1990, 431. (e)
Stang, P. J . Angew. Chem., Int. Ed. Engl. 1992, 31, 274. (f) Prakash,
O.; Saini, N.; Sharma, P. K. Synlett 1994, 221. (g) Kitamura, T. Yuki
Gosei Kagaku Kyokaishi 1995, 53, 893. (h) Stang, P. J .; Zhdankin, V.
V. Chem. Rev. 1996, 96, 1123. (i) Umemoto, T. Chem. Rev. 1996, 96,
1757. (j) Kita, Y.; Takada, T.; Tohma, H. Pure Appl. Chem. 1996, 68,
627. (k) Togo, H.; Hoshina, Y.; Nogami, G.; Yokoyama, M. Yuki Goesi
Kagaku Kyokaishi 1997, 55, 90. (l) Varvoglis, A. Tetrahedron 1997,
53, 1179. (m) Zhdankin, V. V. Rev. Heteroatom Chem. 1997, 17, 133.
(n) Kitamura, T.; Fujiwara, Y. Org. Prep. Proced. Int. 1998, 29, 409.
(o) Varvoglis, A.; Spyroudis, S. Synlett. 1998, 221. (p) Moriarty, R. M.;
Prakash, O. Adv. Heterocycl. Chem. 1998, 69, 1. (q) Togo, H.; Katohgi,
M. Synlett 2001, 565.
10.1021/jo0200670 CCC: $22.00 © 2002 American Chemical Society
Published on Web 05/11/2002

Notes
J . Org. Chem., Vol. 67, No. 12, 2002 4363
Ta ble 2. r-Tosyloxyla tion of Keton es
Ta ble 1. r-Tosyloxyla tin of Acetop h en on e
I(III)
1A
2A
3A
4A
5A
6A
yields (%)
93
38
60
(93)a
98
96
a
Reagent 4A was prepared in situ.
conditions, and the reactivity was compared with that
of the parent compound 1A as shown in Table 1.
The results indicate that compounds 2A and 3A did
not work effectively, while compounds 1A, 4A, 5A, and
6A showed good reactivities with, especially compounds
5A and 6A showing the best reactivity. Thus, π-excess
aromatics retarded the R-tosyloxylation of the ketone.
This result came from the fact that the enol tautomer of
ketone is the reactive species for R-tosyloxylation of
ketone, and its nucleophilic attack to the hypervalent
iodine atoms of [hydroxy(tosyloxy)iodo]arenes is the
second key step.1c Compound 4A was prepared in situ
and used for R-tosyloxylation without purification, be-
cause protonation of the pyrazole nitrogen by p-toluene-
sulfonic acid in the preparation of compounds 4A with
N-tosyl-4-[(diacetoxy)iodo]pyrazole5 and p-toluenesulfonic
acid occurred partly, and its purification was difficult.
In other ketone derivatives, compounds 5A and 6A
showed again the best reactivity among the other [hy-
droxy(tosyloxy)iodo]arenes, as shown in Table 2.
R-Phosphoryloxylation of acetophenone with com-
pounds 2B-6B was carried out, and the reactivity was
compared again with that of the parent compound 1B
as shown in Table 3. Since compounds 2B-6B are
viscous oils and their isolation as a pure state was
difficult, these compounds were used for the R-phosphor-
yloxylation of ketones without isolation. R-Phosphoryl-
oxylation of acetophenone with compounds 1B, 4B, 5B,
and 6B with the in-situ method proceeded effectively.
However, when R-phosphoryloxylation of other ketones
with compounds 1B, 4B, 5B, and 6B was carried out,
compounds 5B and 6B gave the corresponding R-phos-
phoryloxyketones in better yields than those with com-
pounds 1B and 4B as shown in Table 4.
a
b
Reagent 4A was prepared in situ. Solvent: CHCl3 at rt.
c Solvent: CHCl3 at 30 °C.
Ta ble 3. r-P h osp h or yloxyla tion of Acetop h en on e
In conclusion, novel [hydroxy(tosyloxy)iodo]arenes 2A-
6A were prepared, and [hydroxy(phosphoryloxy)iodo]-
arenes 2B-6B were prepared in situ, and R-tosyloxyla-
tion and R-phosphoryloxylation of ketones with these
compounds were carried out, respectively. When their
reactivities were compared with those of the parent
compounds 1A and 1B, respectively, compounds 5A and
6A, and compounds 5B and 6B, showed the best reactiv-
ity. These new hypervalent iodine compounds can be used
as powerful R-tosyloxylation and R-phosphoryloxylation
reagents, instead of the parent compounds 1A and 1B.
I(III)
1B
2B
3B
4B
5B
6B
yields (%)
74 (90)a
63a
86a
89a
97a
97a
a
b
Reagent was prepared in situ. R-Acetoxyacetophenone was
formed in 9% yield as a byproduct.
in hertz. In the 13C NMR spectra, p, s, t, and q means primary,
secondary, tertiary, and quaternary. Melting points were deter-
mined on an electrothermal apparatus in open capillary tubes
and are uncorrected. Wakogel C-200 and Silica Gel 50 (Merck)
were used for column chromatography, Kieselgel 60 F254
(Merck) was used for TLC, and Wakogel B-5F was used for
preparative TLC.
Exp er im en ta l Section
Gen er a l. 1H NMR spectra were recorded on 400 and 500 MHz
spectrometers, 13C NMR spectra were recorded on 100 and 125
MHz spectrometers, and 31P NMR spectra were recorded on 500
Gen er a l P r oced u r e for th e P r ep a r a tion of [Hyd r oxy-
(tosyloxy)iod o]a r en e. A suspension of (diacetoxyiodo)arene (1
mmol) in acetonitrile (2 mL) was added to a solution of
p-toluenesulfonic acid monohydrate (2 mmol) in acetonitrile (2
mL) under an argon atmosphere and stirred for 1 h at room
temperature. After the reaction, the reaction mixture was
filtered, and the solid was washed with diethyl ether or aceto-
nitrile.
1
MHz spectrometer. H NMR and 13C NMR chemical shifts and
31P NMR chemical shifts are expressed in ppm downfield from
TMS and 85% H3PO4 in δ units, respectively. J -Values are given
(5) Togo, H.; Nabana, T.; Yamaguchi, K. J . Org. Chem. 2000, 65,
8391.

4364 J . Org. Chem., Vol. 67, No. 12, 2002
Ta ble 4. r-P h osp h or yloxyla tion of Keton es
Notes
argon atmosphere. Then the reaction mixture was poured into
water and extracted with chloroform twice. The combined
organic layer was dried over Na2SO4. After filtration, the solvent
was evaporated under reduced pressure, and the residue was
purified by preparative TLC on silica gel (eluent: hexane/ethyl
acetate ) 3/1) to give 284 mg of R-tosyloxyacetophenone in 98%
yield.
Typ ica l P r oced u r e for r-Tosyloxyla tion of Acetop h e-
n on e (in situ r ea ction ). To a solution of p-toluenesulfonic acid
monohydrate (2.4 mmol) in acetonitrile (6 mL) was added
N-tosyl-4-[(diacetoxy)iodo]pyrazole (1.2 mmol). The mixture was
stirred for 1 h at room temperature. After the reaction, the
mixture was evaporated under reduced pressure. Then a solution
of acetophenone (1 mmol) in acetonitrile (6 mL) was added to
the residue, and the mixture was refluxed for 4 h under an argon
atmosphere. Then the reaction mixture was poured into water
and extracted with chloroform twice. The combined organic layer
was dried over Na2SO4. After filtration, the solvent was evapo-
rated under reduced pressure, and the residue was purified by
preparative TLC on silica gel (eluent: hexane/ethyl acetate )
3/1) to give 270 mg of R-tosyloxyacetophenone in 93% yield.
r-Tosyloxya cetop h en on e: mp 90 °C (lit.2c mp 90-91 °C);
IR (KBr) 1715, 1360, 1180, 820, 750, 680 cm-1 1H NMR (400
;
MHz, CDCl3) δ ) 2.45 (s, 3H), 5.27 (s, 2H), 7.35 (d, J ) 8.5 Hz,
2H), 7.47 (t, J ) 8.2 Hz, 2H), 7.61 (t, J ) 8.2 Hz, 1H), 7.84 (d, J
) 8.5 Hz, 2H), 7.85 (d, J ) 8.2 Hz, 2H).
r-Tosyloxyp r op iop h en on e: mp 68 °C (lit.2c mp 68-69 °C);
IR (KBr) 1700, 1370, 1170, 830, 760, 660 cm-1 1H NMR (400
;
MHz, CDCl3) δ ) 1.60 (d, J ) 7.0 Hz, 3H), 2.41 (s, 3H), 5.79 (q,
J ) 7.0 Hz, 1H), 7.29 (d, J ) 8.0 Hz, 2H), 7.46 (t, J ) 8.0 Hz,
2H), 7.60 (t, J ) 8.0 Hz, 1H), 7.75 (d, J ) 8.0 Hz, 2H), 7.88 (d,
J ) 8.0 Hz, 2H).
r-Tosyloxycycloh exa n on e: mp 72 °C (lit.2c mp 74-76 °C);
1H NMR (400 MHz, CDCl3) δ ) 1.64-2.60 (m, 6H), 2.44 (s, 3H),
4.90 (dd, J ) 10.8, 5.9 Hz, 1H), 7.34 (d, J ) 8.0 Hz, 2H), 7.84 (d,
J ) 8.0 Hz, 2H).
a
b
Solvent: CHCl3 at rt. Reagent was prepared in situ. c R-
Acetoxyacetophenone was obtained in 9% yield as a byproduct.
d
R-Acetoxypropiophenone was obtained in 24% yield as a byprod-
r-Tosyloxy-2,4-p en ta d ion e: mainly enol tautomer; mp 82
uct. e Reaction time was 4 h. f Reaction time was 6.5 h.
°C (lit.2c mp 82 - 83 °C); IR (KBr) 3060, 1600, 1370, 1200, 1180,
1
800 cm-1; H NMR (400 MHz, CDCl3) δ ) 1.96 (s, 6H), 2.49 (s,
2-[Hyd r oxy(tosyloxy)iod o]th iop h en e 2A. Compound 2A
slowly decomposed when it was dried by vacuum pump for
elemental analysis; 100% yield; mp 65-68 °C (decomp); IR (KBr)
560, 700, 1130, 1190, and 3620 cm-1; 1H NMR (CDCl3 + 3 drops
of CF3CO2H) δ ) 2.43 (3H, s), 7.24 (1H, dd, J ) 5.3 and 3.9 Hz),
7.30 (2H, d, J ) 8.2 Hz), 7.69 (2H, d, J ) 8.2 Hz), 7.80 (1H, dd,
J ) 5.3 and 1.4 Hz), 8.04 (1H, dd, J ) 3.9 and 1.4 Hz).
3-[Hyd r oxy(tosyloxy)iod o]th iop h en e 3A: 87% yield; mp
120-123 °C (decomp.); IR (KBr) 560, 700, 1130, 1190, and 3630
cm-1; 1H NMR (CDCl3 + 3 drops of CF3CO2H) δ ) 2.45 (3H, s),
7.32 (2H, d, J ) 8.1 Hz), 7.60 (1H, dd, J ) 5.3 and 3.0 Hz), 7.66
(1H, dd, J ) 5.3 and 1.2 Hz), 7.69 (2H, d, J ) 8.1 Hz), 8.37 (1H,
dd, J ) 3.0 and 1.2 Hz). Anal. Calcd for C11H11IO4S2: C 33.18;
H 2.78. Found: C 33.16; H 2.77.
N-Tosyl-4-[h yd r oxy(tosyloxy)iod o]p yr a zole 4A: 100%
yield; mp 118-121 °C (decomp); IR (KBr) 820, 1050, 1200, 1310,
1340, and 3450 cm-1; 1H NMR (CDCl3 + 3 drops of CF3CO2H) δ
) 2.45 (3H, s), 2.48 (3H, s), 7.34 (2H, d, J ) 8.2 Hz), 7.43 (2H,
d, J ) 8.3 Hz), 7.71 (2H, d, J ) 8.2 Hz), 7.96 (2H, d, J ) 8.3 Hz).
8.21 (1H, s), 8.82 (1H, s). Anal. Calcd for C17H17N2IO6S2: C 38.07;
H 3.19; N 5.22. Found: C 37.65; H 3.51; N 5.12.
3H), 7.40 (d, J ) 8.1 Hz, 2H), 7.83 (d, J ) 8.1 Hz, 2H), 14.80 (s,
1H).
(Tosyloxy)m eth yl 2-Th ien yl Keton e: mp 92 - 93 °C (lit.2d
mp 94 - 96 °C); IR (KBr) 1685, 1370, 1180, 730 cm-1; 1H NMR
(400 MHz, CDCl3) δ ) 2.45 (s, 3H), 5.09 (s, 2H), 7.16 (dd, J )
5.0, 3.9 Hz, 1H). 7.35 (d, J ) 8.1 Hz, 2H), 7.73 (dd, J ) 5.0, 1.0
Hz, 1H), 7.79 (dd, J ) 3.9, 1.0 Hz, 1H), 7.85 (d, J ) 8.1 Hz, 2H).
(Tosyloxy)m eth yl 2-F u r a n yl Keton e: mp 63 - 64 °C (lit.2c
mp 65-67 °C); IR (KBr) 1695, 1370, 1170, 810, 750 cm-1 1H
;
NMR (400 MHz, CDCl3) δ ) 2.45 (s, 3H), 5.09 (s, 2H), 6.58 (dd,
J ) 3.7, 1.7 Hz, 1H). 7.33 (dd, J ) 3.7, 0.7 Hz, 1H), 7.36 (d, J )
8.2 Hz, 2H), 7.61 (dd, J ) 1.7, 0.7 Hz, 1H), 7.86 (d, J ) 8.2 Hz,
2H).
Typ ica l P r oced u r e for r-P h osp h or yloxyla tion of Aceto-
p h en on e (in situ r ea ction ). To a solution of diphenylphos-
phoric acid (2.4 mmol) and H2O (2.4 mmol) in acetonitrile (3 mL)
was added 3-trifluoromethyl-1-(diacetoxyiodo)benzene (1.2 mmol).
The mixture was stirred for 1 h at room temperature. After the
reaction, the mixture was evaporated under reduced pressure.
Then a solution of acetophenone (1 mmol) in acetonitrile (3 mL)
was added to the residue, and the mixture was refluxed for 3 h
under an argon atmosphere. Then the reaction mixture was
poured into water and extracted with chloroform twice. The
combined organic layer was dried over Na2SO4. After filtration,
the solvent was evaporated under reduced pressure, and the
residue was purified by preparative TLC on silica gel (eluent:
hexane/ethyl acetate ) 4/1) to give 357 mg of R-(diphenylphos-
phoryloxy)acetophenone in 97% yield.
3-Tr iflu or om et h yl-1-[h yd r oxy(t osyloxy)iod o]b en zen e
5A: 91% yield; mp 158-162 °C (decomp); IR (KBr) 690, 800,
1185, 1320, and 3450 cm-1; H NMR (CDCl3 + 3 drops of CF3-
1
CO2H) δ ) 2.44 (3H, s), 7.31 (2H, d, J ) 7.7 Hz), 7.70 (2H, d, J
) 7.7 Hz), 7.78 (1H, t, J ) 8.0 Hz), 8.00 (1H, d, J ) 8.0 Hz),
8.41 (1H, d, J ) 8.0 Hz), 8.42 (1H, s). Anal. Calcd for C14H12F3-
IO4S: C 36.54; H, 2.63. Found: C, 36.49; H, 2.44.
3,5-Bis(tr iflu or om eth yl)-1-[h yd r oxy(tosyloxy)iod o]ben -
zen e 6A: 100% yield; mp 89-91 °C (decomp); IR (KBr) 700,
820, 1190, 1350, and 3400 cm-1;1H NMR (CDCl3) δ ) 2.34 (3H,
s), 7.09 (2H, d, J ) 8.0 Hz), 7.48 (2H, d, J ) 8.0 Hz), 7.89 (1H,
s), 8.61 (2H, s). Anal. Calcd for C15H11F6IO4S: C, 34.11; H, 2.10.
Found: C, 34.19; H, 1.86.
Typ ica l P r oced u r e for r-Tosyloxyla tion of Acetop h e-
n on e. To a solution of acetophenone (1 mmol) in acetonitrile (6
mL) was added 3-trifluoromethyl-1-[hydroxy(tosyloxy)iodo]ben-
zene (1.2 mmol). The mixture was refluxed for 4 h under an
r-(Dip h en ylp h osp h or yloxy)a cetop h en on e: oil; IR (neat)
1
700, 760, 1270, and 1710 cm-1; H NMR (CDCl3) δ ) 5.45 (2H,
d, J H-P ) 9.9 Hz), 7.16-7.37 (10H, m), 7.42-7.49 (2H, m), 7.56-
7.62 (1H, m), 7.86-7.89 (2H, m); 13C NMR (CDCl3) δ ) 69.9 (s,
J C-P ) 6 Hz), 120.2 (t, J C-P ) 5 Hz), 125.5 (t), 127.8 (t), 128.9
(t), 129.8 (t), 133.7 (q), 134.1 (t), 150.4 (q, J C-P ) 7 Hz), 190.8
(q); 31P NMR (CDCl3) δ ) -12.98; HRMS (FAB) Found m/z )
369.0912, Calcd for C20H18O5P M + 1 ) 369.0814.
r-(Dip h en ylp h osp h or yloxy)cycloh exa n on e: oil; IR (neat)
690, 770, 1285, and 1740 cm-1; 1H NMR (CDCl3) δ ) 1.57-2.03

Notes
J . Org. Chem., Vol. 67, No. 12, 2002 4365
(5H, m), 2.28-2.36 (2H, m), 2.52-2.56 (1H, m), 4.96-5.03 (1H,
m), 7.14-7.36 (10H, m); 13C NMR (CDCl3) δ ) 23.3 (s), 26.8 (s),
34.9 (s, J C-P ) 4 Hz), 40.4 (s), 81.4 (t, J C-P ) 7 Hz), 120.2 (t,
J C-P ) 5 Hz), 120.3 (t, J C-P ) 5 Hz), 125.2 (t), 125.4 (t), 129.6 (t,
J C-P ) 9 Hz), 129.7 (t, J C-P ) 9 Hz), 150.3 (q, J C-P ) 7 Hz),
150.5 (q, J C-P ) 7 Hz), 203.7 (q); 31P NMR (CDCl3) δ ) -13.07;
HRMS (FAB) Found m/z ) 347.1054, Calcd for C18H20O5P M +
1 ) 347.0970.
Hz); 13C NMR (CDCl3) δ ) 69.6 (s, J C-P ) 6 Hz),120.2 (t, J C-P
)
5 Hz), 125.6 (t), 128.4 (t), 129.9 (t), 132.5 (t), 134.8 (t), 139.9 (q),
150.4 (q, J C-P ) 7 Hz), 184.1 (q); 31P NMR (CDCl3) δ ) -12.26;
HRMS (FAB) Found m/z ) 375.0428, Calcd for C18H16SPO5
+ 1 ) 375.0378.
M
Ack n ow led gm en t. Financial support from a Grant-
in-Aid for Scientific Research (No. 13554028) from the
Ministry of Education, Science, Sports and Culture of
J apan is gratefully acknowledged. We thank Ms. Rit-
suko Hara for the measurements of HRMS and Dr.
Hiroko Seki and Ms. Yukiko Hiramoto for the measure-
ments of elemental analysis in the Chemical Analysis
Center of Chiba University.
r-(Dip h en ylp h osp h or yloxy)p r op iop h en on e: oil; IR (neat)
1
690, 770, 1280, and 1700 cm-1; H NMR (CDCl3) δ ) 1.61 (3H,
d, J ) 6.8 Hz), 5.91 (1H, qd, J ) 6.8 Hz, J H-P ) 6.7 Hz), 7.13-
7.37 (10H, m), 7.42-7.46 (2H, m), 7.53-7.60 (1H, m), 7.91-7.93
(2H, m); 13C NMR (CDCl3) δ ) 19.3 (p, J C-P ) 5 Hz), 76.4 (t,
J C-P ) 6 Hz), 115.3 (t), 120.2 (t, J C-P ) 5 Hz), 125.5 (t, J C-P
)
6 Hz), 128.8 (t, J C-P ) 3 Hz), 129.5 (q), 129.7 (t, J C-P ) 11 Hz),
133.7 (t), 150.3 (q), 195.2 (q); 31P NMR (CDCl3) δ ) -12.98;
HRMS (FAB) Found m/z ) 383.1014, Calcd for C21H20O5P M +
1 ) 383.0970.
1
Su p p or tin g In for m a tion Ava ila ble: Copies of H NMR
r-(Dip h en ylp h osp h or yloxy)-2-a cetylth iop h en e: oil; IR
(neat) 690, 730, 760, 780, 1290, and 1680 cm-1; 1H NMR (CDCl3)
δ ) 5.31 (2H, d, J H-P ) 9.7 Hz), 7.13 (1H, dd, J ) 4.8 and 3.9
Hz), 7.17-7.23 (2H, m), 7.25-7.30 (4H, m), 7.33-7.37 (4H, m),
7.71 (1H, dd, J ) 4.8 and 1.0 Hz), 7.73 (1H, dd, J ) 3.9 and 1.0
spectra for compounds 2A-6A and all R-tosyloxyketones and
R-phosphoryloxy ketones. This material is available free of
charge via the Internet at http://pubs.acs.org.
J O0200670