A new route for generation of α-λ3-iodanyl ketones via ester exchange of (Z)-(β-acetoxyvinyl)-λ3-iodanes: Their nucleophilic substitutions with halides and sulfur and phosphorus nucleophiles

Article abstract of DOI:10.1021/jo0107711

An efficient method for generation of α-λ³-iodanyl ketones from (Z)-(2-acetoxyvinyl)(phenyl)-λ³-iodanes was developed. The method involves ester exchange of (Z)-2-acetoxyvinyl-λ³-iodanes with methanol in the presence of triethylamine. α-λ³Iodanyl ketones react with a variety of nucleophiles such as halides, thiols, phosphines, phosphinic acids, and phosphates, under the conditions which produce α-functionalized carbonyl compounds probably via an S_N2 pathway.

Full text of DOI:10.1021/jo0107711

J . Org. Chem. 2002, 67, 4407-4413
4407
A New Rou te for Gen er a tion of r-λ3-Iod a n yl Keton es via Ester
Exch a n ge of (Z)-(â-Acetoxyvin yl)-λ3-iod a n es: Th eir Nu cleop h ilic
Su bstitu tion s w ith Ha lid es a n d Su lfu r a n d P h osp h or u s
Nu cleop h iles
Masahito Ochiai,* J unichi Nishitani, and Yoshio Nishi
Faculty of Pharmaceutical Sciences, University of Tokushima,
1-78 Shomachi, Tokushima 770-8505, J apan
mochiai@ph2.tokushima-u.ac.jp
Received J uly 31, 2001
An efficient method for generation of R-λ3-iodanyl ketones from (Z)-(2-acetoxyvinyl)(phenyl)-λ3-
iodanes was developed. The method involves ester exchange of (Z)-2-acetoxyvinyl-λ3-iodanes with
methanol in the presence of triethylamine. R-λ3-Iodanyl ketones react with a variety of nucleophiles
such as halides, thiols, phosphines, phosphinic acids, and phosphates, under the conditions which
produce R-functionalized carbonyl compounds probably via an SN2 pathway.
OP(O)(OPh)2,10 OP(O)R2,11 and N3 can be generated in
12
In tr od u ction
situ from carbonyl compounds or silyl enol ether deriva-
tives by the reaction with λ3-organoiodanes. In most of
these organoiodanes 1, the ligand X is introduced to
the R-carbon atom of the carbonyl compounds regio-
selectively with reductive elimination of iodobenzene.
R-λ3-Iodanyl ketones 1 with BF4 as ligand X are known
and react with a variety of carbon nucleophiles in-
cluding silyl enol ethers, olefins, and allylsilanes.13
Oxidation of alkynes with λ3-organoiodanes is an efficient
alternative for generation of R-λ3-iodanyl ketones 1 and
affords R-hydroxy, R-trifluoroacetoxy, and R-phosphoryl-
oxy ketones and/or their further oxidation prod-
ucts.14-16
It has been generally accepted that R-λ3-iodanyl ke-
tones of general structure 1 are key intermediates in the
oxidation of carbonyl compounds at the R-carbon atom
by λ3-organoiodanes under acidic and basic conditions.1
For instance, (diacetoxyiodo)benzene brings about oxida-
tion of ketones in acetic acid-acetic anhydride in the
presence of sulfuric acid to give R-acetoxy ketones, in
which intermediate formation of R-λ3-iodanyl ketones 1
(X ) OAc) is believed to be involved.2 R-λ3-Iodanyl ketones
1 are highly reactive toward the attack of nucleophiles,
probably via an SN2 pathway with reductive elimination
of iodobenzene, and thus have never been isolated.3 This
is due to the very high nucleofugality of the λ3-phen-
yliodanyl groups, which show a leaving group ability
about 106 times greater than that of the superleaving
group, triflate.4
(5) (a) Moriarty, R. M.; Hu, H.; Gupta, S. C. Tetrahedron Lett. 1981,
22, 1283. (b) Moriarty, R. M.; Hou, K.-C. Tetrahedron Lett. 1984, 25,
691. (c) Moriarty, R. M.; Prakash, O.; Freeman, W. A. J . Chem. Soc.,
Chem. Commun. 1984, 927. (d) Moriarty, R. M.; Engerer, S. G.;
Prakash, I.; Gill, U. S.; Freeman, W. A. J . Chem. Soc., Chem. Commun.
1985, 1715.
(6) Moriarty, R. M.; Rani, N.; May, E. J .; Guo, L.; Prakash, O. J .
Chem. Res., Synop. 1998, 32.
(7) (a) Moriarty, R. M.; Hu, H. Tetrahedron Lett. 1981, 22, 2747. (b)
Tamura, Y.; Yakura, T.; Shirouchi, Y.; Haruta, J . Chem. Pharm. Bull.
1985, 33, 1097.
(8) Moriarty, R. M.; Berglund, B. A.; Penmasta, R. Tetrahedron Lett.
1992, 33, 6065.
(9) Lodaya, J . S.; Koser, G. F. J . Org. Chem. 1988, 53, 210.
(10) Koser, G. F.; Lodaya, J . S.; Ray, D. G.; Kokil, P. B. J . Am. Chem.
Soc. 1988, 110, 2987.
(11) Moriarty, R. M.; Condeiu, C.; Tao, A.; Prakash, O. Tetrahedron
Lett. 1997, 38, 2401.
(12) Moriarty, R. M.; Vaid, R. K.; Ravikumar, V. T.; Vaid, B. K.;
Hopkins, T. E. Tetrahedron 1988, 44, 1603.
R-λ3-Iodanyl ketones 1 with various heteroatom lig-
ands such as OH,5 OMe,6 OAc,7 OCOCF3,8 OTs,3 OMs,9
(1) (a) Moriarty, R. M.; Prakash, O. Acc. Chem. Res. 1986, 19, 244.
(b) Moriarty, R. M.; Vaid, R. K.; Koser, G. F. Synlett 1990, 365. (c)
Moriarty, R. M.; Vaid, R. K. Synthesis 1990, 431. (d) Varvoglis, A. The
Organic Chemistry of Polycoordinated Iodine; VCH Publishers: New
York, 1992.
(2) Mizukami, F.; Ando, M.; Tanaka, T.; Imamura, J . Bull. Chem.
Soc. J pn. 1978, 51, 335.
(13) (a) Zhdankin, V. V.; Tykwinski, R.; Caple, R.; Berglund, B.;
Kozmin, A. S.; Zefirov, N. S. Tetrahedron Lett. 1988, 29, 3703. (b)
Zhdankin, V. V.; Mullikin, M.; Tykwinski, R.; Berglund, B.; Caple, R.;
Zefirov, N. S.; Kozmin, A. S. J . Org. Chem. 1989, 54, 2605. (c) Zefirov,
N. S.; Samoniya, N. S.; Kutateladze, T. G.; Zhdankin, V. V. Zh. Org.
Khim. 1991, 27, 220.
(14) (a) Merkushev, E. B.; Karpitskaya, L. G.; Novosel’tseva, G. I.
Dokl. Akad. Nauk SSSR 1979, 245, 607. (b) Tamura, Y.; Yakura, T.;
Haruta, J .; Kita, Y. Tetrahedron Lett. 1985, 26, 3837. (c) Vasil’eva, V.
P.; Khalfina, I. L.; Karpitskaya, L. G.; Merkushev, E. B. Zh. Org. Khim.
1987, 23, 2225. (d) Moriarty, R. M.; Penmasta, R.; Awasthi, A. K.;
Prakash, I. J . Org. Chem. 1988, 53, 6124. (e) Haruta, J .; Nishi, K.;
Matsuda, S.; Akai, S.; Tamura, Y.; Yakura, T.; Kita, Y. J . Org. Chem.
1990, 55, 4853.
(3) R-λ3-Iodanyl â-diketones are known. 2-Dimedonyl(phenyl)iodo-
nium tosylate has been prepared from dimedone by the reaction with
[hydroxy(tosyloxy)iodo]benzene in good yield as a white solid, which
on heating in acetonitrile affords 2-tosyloxydimedone. See: Koser, G.
F.; Relenyi, A. G.; Kalos, A. N.; Rebrovic, L.; Wettach, R. H. J . Org.
Chem. 1982, 47, 2487.
(4) The leaving process of λ3-phenyliodanyl groups involves an
energetically favorable reduction of the hypervalent iodine(III) to the
normal valency (i.e., PhI) with octet structure. This is the origin of
the high leaving group ability. Therefore, a nucleofuge such as the λ3-
aryliodanyl group is termed a hyperleaving group. See: (a) Ochiai, M.
In Chemistry of Hypervalent Compounds; Akiba, K., Ed.; Wiley-VCH:
New York, 1999; Chapter 12. (b) Okuyama, T.; Takino, T.; Sueda, T.;
Ochiai, M. J . Am. Chem. Soc. 1995, 117, 3360.
(15) Koser, G. F.; Chen, X.; Chen, K.; Sun, G. Tetrahedron Lett. 1993,
34, 779.
10.1021/jo0107711 CCC: $22.00 © 2002 American Chemical Society
Published on Web 06/04/2002

4408 J . Org. Chem., Vol. 67, No. 13, 2002
Ochiai et al.
Sch em e 1
Sch em e 2
Sch em e 3
Recently, we found that ester exchange between (Z)-
(2-acetoxyvinyl)(phenyl)-λ3-iodanes 2 (X ) BF4) and
EtOLi in THF at -78 °C generates monocarbonyl iodo-
nium ylides 3 quantitatively with liberation of ethyl
acetate (Scheme 1).17 The monocarbonyl iodonium ylides
3 are moderately nucleophilic and undergo alkylidene
transfer to aldehydes and activated imines to give R,â-
epoxy ketones and 2-acylaziridines stereoselectively in
good yields. On the basis of the reported data that the
introduction of the λ3-phenyliodanyl group raises the CH
acidity of malonic esters by approximately 8 orders of
magnitude,18 the acidity (pKa) of the R-methylene protons
of R-λ3-iodanyl ketones 1 (R2 ) H) would be estimated to
be around 12. In fact, iodonium ylide 3a (R ) n-C8H17
)
still survives even in the presence of excess amounts of
ethanol with a pKa value of 15.9 and reacts with benzal-
dehyde, yielding the corresponding R,â-epoxy ketone
under these conditions.17a
mechanism for the reaction is shown in Scheme 3. High-
yield formation of methyl acetate clearly indicates the
intervention of ester exchange between â-acetoxyvinylio-
dane 2a and MeOH to produce monocarbonyl iodonium
ylide 3. The Et3NHBF4 (pKa ) 11.0) produced during the
reaction undergoes proton transfer to the iodonium ylide
3, yielding R-λ3-iodanyl ketone 9.20 Alternatively, R-λ3-
iodanyl ketone 9 might be directly produced via triethy-
lamine-mediated ester exchange of vinyliodanes 2a with
MeOH. Nucleophilic attack of methanol on R-iodanyl
ketone 9 at the R-position gives rise to the R-methoxy
ketone 4, probably via an SN2 pathway. On the other
hand, attack of methanol upon the carbonyl group of 9
produces hemiacetal 10, which, in turn, undergoes in-
tramolecular reductive cyclization with formation of
epoxide 11. The oxirane 11 would be attacked by another
methanol at the acetal carbon atom with formation of
R-hydroxy dimethyl acetal 5. R-Methoxy ketone 4 might
also be produced by nucleophilic attack of methanol at
the other carbon atom of the oxirane ring of 11.
The mechanism for formation of R-hydroxy dimethyl
acetal 5 from R-λ3-iodanyl ketone 9, shown in Scheme 3,
was originally proposed by Moriarty and co-workers in
the oxidation of ketones with (diacetoxyiodo)benzene in
alkaline methanol.5 They demonstrated that the label
(18O) of the carbonyl oxygen of the ketones was incorpo-
rated into the hydroxyl group of the R-hydroxy dimethyl
acetal 5 produced.1a
In dichloromethane, the major product (2-oxoalkyl)-
ammonium salt 6 will be produced probably via an SN2
displacement of ketone 9 by triethylamine. The solvent
dichloromethane may also act as a nucleophile in SN2
displacement of ketone 9, yielding R-chloro ketone 7a .
Dichloromethane can react with a highly electron-
deficient species, such as a carbenoid and a carbocation,
We envisioned that generation of the monocarbonyl
iodonium ylides 3 in the presence of an appropriate
proton source with similar acidity (pKa ) 12) makes it
possible to protonate the iodonium ylides 3, producing
R-λ3-iodanyl ketones 1 (R2 ) H). We now report a method
for in situ generation of R-λ3-iodanyl ketones 1 from (Z)-
(2-acetoxyvinyl)(phenyl)-λ3-iodanes 2 (X ) BF4) via ester
exchange reaction of the â-acetoxy group, and their
nucleophilic substitutions with halides and sulfur and
phosphorus nucleophiles.19
Resu lts a n d Discu ssion
Gen er a tion of r-λ3-Iod a n yl Keton es. Exposure of
(Z)-(2-acetoxy-1-decenyl)(phenyl)-λ3-iodane 2a (X ) BF4)
to triethylamine (1.1 equiv) in MeOH at room tempera-
ture for 1 h gave R-methoxy ketone 4 (43%) and R-hy-
droxy dimethyl acetal 5 (35%), along with the formation
of methyl acetate (91%). Without triethylamine, 2a was
quantitatively recovered unchanged. Interestingly, chang-
ing the solvent from methanol to dichloromethane re-
sulted in a decrease in the rate of the reaction (at room
temperature for 5 h) and gave a mixture of products: (2-
oxoalkyl)triethylammonium tetrafluoroborate 6 (44%),
R-chloro ketone 7a (14%), and R-acetoxy ketone 8 (4%)
(Scheme 2).
Formation of R-methoxy ketone 4 and R-hydroxy di-
methyl acetal 5 in methanol strongly suggests the
intermediacy of R-λ3-iodanyl ketone 9, and a possible
(16) Ochiai, M.; Kunishima, M.; Fuji, K.; Nagao, Y. J . Org. Chem.
1989, 54, 4038.
(17) (a) Ochiai, M.; Kitagawa, Y.; Yamamoto, S. J . Am. Chem. Soc.
1997, 119, 11598. (b) Ochiai, M.; Kitagawa, K. Tetrahedron Lett. 1998,
39, 5569. (c) Ochiai, M.; Kitagawa, Y. J . Org. Chem. 1999, 64, 3181.
(18) Neiland, O. Y.; Karele, B. Y. Zh. Org. Khim. 1971, 7, 1611.
(19) A part of this work has been reported in a preliminary form:
Ochiai, M.; Nishi, Y.; Nishitani, J .; Chen, D.-W.; Hashimoto, S.;
Tsuchimoto, Y. J . Chem. Soc., Chem. Commun. 2000, 1157.
(20) Lide, D. R. CRC Handbook of Chemistry and Physics; CRC:
Boca Raton, FL, 1992.

Generation of R-λ3-Iodanyl Ketones
J . Org. Chem., Vol. 67, No. 13, 2002 4409
Ta ble 1. Nu cleop h ilic Su bstitu tion of r-λ3-Iod a n yl
Sch em e 4
Keton es 9 w ith Ha lid esa
2
equiv of
Et3N
time R-halo yield
entry (X ) BF4)
halide solvent
(h) ketone (%)b
1
2
3
4
5
6
7
8
9
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
2a
2b
1.1
1.1
1.1
1.1
1.1
1.1
0.2
NaF
NaCl
NaBr
NaI
Bu4NCl MeOH
Bu4NBr MeOH
Bu4NBr MeOH
Bu4NBr MeOH
Bu4NBr CH2Cl2
Bu4NBr CH2Cl2
MeOH
MeOH
MeOH
MeOH
3
1
1
1
1
1
24
1
9
1
14a
7a
15a
16a
7a
15a
15a
15a
15a
15a
16a
15b
0c
63
85
71
69
84
71
33d
50
75f
71
64
Sch em e 5
1.1
1.1
1.1
1.1
e
10
11
12
Bu4NI
Bu4NBr MeOH
MeOH
1
1
a
Reactions were carried out using 1.2 equiv of a halide at 25
°C under nitrogen. Isolated yields. c R-Methoxy ketone 4 (47%)
b
and transfer the chlorine atom.21 The presence both of
the strongly electron-withdrawing λ3-phenyliodanyl group
with a large Hammett σ value (σp ) 1.37)22 and of the
acyl group makes the R-carbon atom of 9 highly electron-
deficient, and thereby nucleophile displacement of ketone
9 with dichloromethane becomes possible.
Triethylamine readily abstracts an R-vinylic hydrogen
of simple vinyl(phenyl)-λ3-iodane 12 to produce 1-decyne
via the intermediacy of alkylidene carbene 13 (Scheme
4).23 This R-elimination pathway was not detected for
reactions of â-acetoxyvinyliodane 2a . This is probably due
to the presence of the â-acetoxy group in 2a . We believe
that the electron-withdrawing λ3-phenyliodanyl group of
2a highly activates the ester carbonyl group toward the
attack of nucleophiles,22 which makes the triethylamine-
catalyzed ester exchange with methanol more facile than
the R-elimination pathway.
d
and R-hydroxy dimethyl acetal 5 (33%) were obtained. Iodane
2a (53%) was recovered. e Reaction was carried out in the presence
of benzyl alcohol (5 equiv). f Benzyl acetate (66%) was obtained.
Ta ble 2. Su bstitu tion of r-λ3-Iod a n yl Keton es 9 w ith
Su lfu r Nu cleop h ilesa
2
nucleophile
(equiv)
yield
entry (X ) BF4) base
solvent product (%)b
1
2
3
4
5
2a
2a
2a
2b
2c
Et3N PhSH (2)
Et3N PhSO2Na (3) MeOH
EtOLi PhSH (3)
EtOLi PhSH‘ (3)
EtOLi PhSH (3)
MeOH
17a
18a
17a
17b
17c
36c
56d
65
77
78
THFe
THFe
THFe
a
Reactions were carried out using 1.1 equiv of a base at 0 °C
for 1 h under nitrogen. Isolated yields. c â-Acetoxyvinyl iodide
b
d
19 (19%) and terminal olefin 20 (20%) were obtained. R-Hydroxy
dimethyl acetal 5 (15%) was obtained. e Reaction temperature -78
°C to room temperature.
Nu cleop h ilic Su bstitu tion w ith Ha lid es. When
R-λ3-iodanyl ketones 9 were generated from (Z)-2-ace-
toxyvinyliodanes 2 (X ) BF4) by the room temperature
reaction with triethylamine-MeOH in the presence of
sodium or tetrabutylammonium halides, nucleophilic
substitution took place, and R-halo ketones (R-chloro 7,
R-bromo 15, and R-iodo 16) were obtained in good yields
(Scheme 5, Table 1). In the reaction with sodium fluoride,
no substitution with fluoride was observed, but instead,
large amounts of R-methoxy ketone 4 and R-hydroxy
dimethyl acetal 5 were formed (Table 1, entry 1). Very
interestingly, even without triethylamine, iodanyl ketone
9 is apparently generated in methanol and produces
R-bromo ketones 15, although the rate of the reaction
seems to slow considerably (compare Table 1, entries
6-8). In addition to R-bromo ketone 15a (75%), formation
of benzyl acetate (66%) in the reaction of 2a in the
presence of benzyl alcohol in dichloromethane provides
additional evidence for the ester exchange mechanism
(Table 1, entry 10).
Sch em e 6
Nu cleop h ilic Su bstitu tion w ith Su lfu r Nu cleo-
p h iles. Reaction of λ3-iodanes 2 in the presence of
thiophenol as a nucleophile gave a mixture of products:
treatment of 2a with triethylamine in MeOH in the
presence of thiophenol (2 equiv) at 0 °C afforded the
desired sulfide 17a , but in only 36% yield (Table 2, entry
1). In this reaction, large amounts of (Z)-â-acetoxyvinyl
iodide 19 (19%) and terminal olefin 20 (20%) were also
obtained. The use of sodium benzenesulfinate (3 equiv)
as a nucleophile afforded â-keto sulfone 18a in moderate
yield (56%) (Scheme 6).
The formation of olefins 19 and 20 suggests the
simultaneous occurrence of another process that com-
petes with the desired ester exchange reaction of 2a . The
competing reaction probably involves a single-electron
transfer to highly electron-deficient λ3-iodane 2a , gener-
It has been reported that exposure of stable iodonium
ylides, derived from 1,3-diketones, to hydrochloric acid
in methanol results in the formation of 2-chloro 1,3-
diketones via nucleophilic substitution on the intermedi-
ate 2-(λ3-phenyliodanyl) 1,3-diketones with chloride.24,25
(21) (a) White, E. H.; McGirk, R. H.; Aufdermarsh, C. A.; Tiwari,
H. P.; Todd, M. J . J . Am. Chem. Soc. 1973, 95, 8107. (b) Pirrung, M.
C.; Zhang, J .; Lackey, K.; Sternbach, D. D. Brown, F. J . Org. Chem.
1995, 60, 2112.
(22) Mironova, A. A.; Maletina, I. I.; Iksanova, S. V.; Orda, V. V.;
Yagupolskii, L. M. Zh. Org. Chem. 1989, 25, 306.
(23) (a) Ochiai, M.; Takaoka, Y.; Nagao, Y. J . Am. Chem. Soc. 1988,
110, 6565. (b) Ochiai, M.; Kunishima, M.; Tani, S.; Nagao, Y. J . Am.
Chem. Soc. 1991, 113, 3135. (c) Ochiai, M.; Sueda, T.; Uemura, K.;
Masaki, Y. J . Org. Chem. 1995, 60, 2624.
(24) (a) Neiland, O. Zh. Org. Khim. 1965, 1, 1858. (b) Coats, S. J .;
Wasserman, H. H. Tetrahedron Lett. 1995, 36, 7735.
(25) Interestingly, Hara and Yoneda reported direct fluorination of
â-ketoesters using p-(difluoroiodo)toluene and a HF-pyridine complex.
Hara, S.; Sekiguchi, M.; Ohmori, A.; Fukuhara, T.; Yoneda, N. J . Chem.
Soc., Chem. Commun. 1996, 1899.

4410 J . Org. Chem., Vol. 67, No. 13, 2002
Ochiai et al.
Sch em e 7
with aldehydes (Scheme 9). The formation of phospho-
nium ylide 28 is compatible with the reported acidity of
acetonyl(triphenyl)phosphonium salt 22d (R ) Me, pKa
) 6.6), more acidic than Et3NHBF4.29 We have reported
that, after treatment of 2 with triethylamine in the
presence of triphenylphosphine in MeOH at room tem-
perature, addition of an aldehyde to the reaction mixture
and then heating at 60 °C resulted in the formation of
R,â-unsaturated ketones with high trans selectivity.19
The nucleophilicity of diphenylphosphinic acid seems
to be lower than that of triphenylphosphine: thus,
reaction of 2a (X ) BF4) with triethylamine and diphen-
ylphosphinic acid in MeOH gave the desired R-ketol
diphenylphosphinate 23a in only 18% yield (Table 3,
entry 4). In this reaction, the solvent methanol rather
than diphenylphosphinic acid acts as a major nucleophile
toward R-λ3-iodanyl ketone 9, and large amounts of
R-methoxy ketone 4 (38%) and R-hydroxy dimethyl acetal
5 (15%) were produced. Nucleophilic attack of methanol
on R-λ3-iodanyl ketone 9 is reduced to a negligibly small
extent by using both dichloromethane as a solvent
instead of methanol and limited amounts of methanol (2
equiv). Under these conditions, R-ketol diphenylphosphi-
nate 23a was obtained in 78% yield (Table 3, entry 5).
Vinyl-λ3-iodanes 2b and 2c were also converted into ketol
diphenylphosphinates 23b and 23c in high yields.
Similarly, the reaction with dimethylphosphinic acid
afforded R-ketol dimethylphosphinates 24a -c in yields
of 77-98% (Table 3, entries 8-10). Dimethylphosphinate
24 seems to be labile toward hydrolysis,30 and in fact,
partial hydrolysis of 24 was observed on purification by
silica gel thin-layer chromatography.
Sch em e 8
ating the vinyl(phenyl)iodanyl radical 21 (Scheme 7).26,27
Radical 21 would decompose by two paths, one leading
to phenyl radical and â-acetoxyvinyl iodide 19, and the
other to â-acetoxyvinyl radical and iodobenzene. â-Ac-
etoxyvinyl radical abstracts a hydrogen atom from thiophe-
nol and affords the terminal olefin 20. Single-electron
transfer does not seem to be important in the reaction
with sodium benzenesulfinate, which gives â-keto sulfone
18a in moderate yield.
To avoid the undesirable single-electron transfer, the
monocarbonyl iodonium ylide 3 was pregenerated from
2 by the reaction with EtOLi in THF, prior to the addition
of thiophenol. It is likely that the addition of thiophenol
with a pKa value of 8.428 can cause rapid protonation of
the ylide 3 with formation of the R-λ3-iodanyl ketone 9,
which reacts with thiophenol or its anion to give â-keto
sulfide 17. This alternative procedure was found to
exclusively inhibit the competing single-electron-transfer
process and afforded the desired â-keto sulfides 17a -c
in good yields (Table 2, entries 3-5).
Nu cleop h ilic Su bstitu tion w ith P h osp h or u s Nu -
cleop h iles. R-λ3-Iodanyl ketones 9 also undergo substi-
tutions by the reaction with phosphorus nucleophiles,
such as phosphines, phosphinic acids, and phosphates
(Scheme 8). Treatment of 2a (X ) BF4) with triethyl-
amine in the presence of triphenylphosphine (2 equiv)
in MeOH at room temperature, after acidification of the
reaction mixture with 5% aqueous HBF4 solution, af-
forded (2-oxodecyl)phosphonium tetrafluoroborate 22a in
89% yield. â-Keto phosphonium salts 22b and 22c were
also obtained in good yields (Table 3, entries 1-3).
In these reactions, â-keto phosphonium ylide 28 seems
to be produced, which makes possible Wittig olefination
Diphenyl, dibenzyl, and dibutyl phosphates also un-
derwent SN2 displacement of R-λ3-iodanyl ketone 9 in
dichloromethane in the presence of methanol (2 equiv)
and afforded R-phosphoryloxy ketones 25-27 in good to
excellent yields (Table 3, entries 11-17). However, at-
tempted nucleophilic substitutions of 9 with trimethyl
phosphite, yielding â-keto phosphonates,31 and with
trimethyl phosphate, yielding R-ketol phosphate,32 were
found to be fruitless.
R-Phosphoryloxy ketones have been prepared by Koser
and co-workers by direct R-oxyphosphorylation of ketones
using phosphoryloxy(phenyl)-λ3-iodanes 29 and 30.10,33
The direct R-oxyphosphorylation of ketones was proposed
to involve nucleophilic substitution of R-λ3-iodanyl ke-
tones, generated in situ, with diphenyl and dibenzyl
phosphates. R-Ketol dimethylphosphinates and diphen-
ylphosphinates were prepared by R-phosphinylation of
carbonyl compounds using λ3-phenyliodanes 31 and 32.11
In conclusion, we have developed a new, efficient
(26) For nomenclature, see: Perkins, C. W.; Martin, J . C.; Arduengo,
A. J .; Lau, W.; Alegria, A.; Kochi, J . K. J . Am. Chem. Soc. 1980, 102,
7753.
method for in situ generation of R-λ3-iodanyl ketones from
(27) For generation of [9-I-2] iodanyl radicals, see: (a) Chen, D.-
W.; Ochiai, M. J . Org. Chem. 1999, 64, 6804. (b) Ochiai, M.; Ito, T.;
Takahashi, H.; Nakanishi, A.; Toyonari, M.; Sueda, T.; Goto, S.; Shiro,
M. J . Am. Chem. Soc. 1996, 118, 7716. (c) Tanner, D. D.; Reed, D. W.;
Setiloane, B. P. J . Am. Chem. Soc. 1982, 104, 3917. (d) Beringer, F.
M.; Falk, R. A. J . Chem. Soc. 1964, 4442. (e) Crivello, J . V. Adv. Polym.
Sci. 1984, 62, 1. (f) Kampmeier, J . A.; Nalli, T. W. J . Org. Chem. 1993,
58, 943. (g) Mubarak, M. S.; Peters, D. G. J . Org. Chem. 1985, 50,
673.
(28) Oae, S. Organic Chemistry of Sulfur; Plenum: New York, 1977.
(29) (a) Fliszar, S.; Hudson, R. F.; Salvadori, G. Helv. Chim. Acta
1963, 46, 1580. (b) J ohnson, A. W.; Amel, R. T. Can. J . Chem. 1968,
46, 461.
(30) Ramirez, F.; Marecek, J . F. Synthesis 1985, 449.
(31) Kim, D. Y.; Mang, J . Y.; Oh, D. Y. Synth. Commun. 1994, 24,
629.
(32) Popov, K. A.; Polozov, A. M.; Tcherezov, S. V. Tetrahedron Lett.
1997, 38, 1859.

Generation of R-λ3-Iodanyl Ketones
J . Org. Chem., Vol. 67, No. 13, 2002 4411
Ta ble 3. Su bstitu tion of r-λ3-Iod a n yl Keton es 9 w ith P h osp h or u s Nu cleop h ilesa
2
equiv of
Et3N
nucleophile
(equiv)
additive
(equiv)
time
(h)
yield
(%)b
entry
(X ) BF4)
solvent
product
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
2a
2b
2c
2a
2a
2b
2c
2a
2b
2c
2a
2a
2b
2c
2a
2b
2c
1.1
1.1
1.1
2.5
1.1
1.1
1.1
1.1
1.1
1.1
2.0
2.0
2.0
2.0
2.0
2.0
2.0
Ph3P (2)
Ph3P (2)
Ph3P (2)
Ph2P(O)OH (1.2)
Ph2P(O)OH (2)
Ph2P(O)OH (2)
Ph2P(O)OH (2)
Me2P(O)OH (2)
Me2P(O)OH (2)
MeOH
MeOH
MeOH
MeOH
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
CH2Cl2
1
1
1
22a
22b
22c
23a
23a
23b
23c
24a
24b
24c
25a
26a
26b
26c
27a
27b
27c
89
66
53(96)c
18d
78
1
MeOH (2)
MeOH (2)
MeOH (2)
MeOH (2)
MeOH (2)
MeOH (2)
MeOH (2)
MeOH (2)
MeOH (2)
MeOH (2)
MeOH (2)
MeOH (2)
MeOH (2)
17
48
24
6
4
6
96
48
21
35
7
87
88
98
93c
77(100)c
47c
83
Me2P(O)OH (2)
(PhO)2P(O)OH (2)
(PhCH2O)2P(O)OH (2)
(PhCH2O)2P(O)OH (2)
(PhCH2O)2P(O)OH (2)
(n-BuO)2P(O)OH (2)
(n-BuO)2P(O)OH (2)
(n-BuO)2P(O)OH (2)
84
71
80
69
25
6
64
a
b
d
Reactions were carried out at 25 °C under nitrogen. Isolated yields. c 1H NMR yields. R-Methoxy ketone 4 (38%) and R-hydroxy
dimethyl acetal 5 (15%) were obtained.
0.062 mmol) in methanol (1.5 mL) was added triethylamine
(6.9 mg, 0.068 mmol) under nitrogen at room temperature, and
the mixture was stirred for 1 h. After addition of water,
methanol was evaporated under an aspirator vacuum. The
mixture was extracted with dichloromethane, and the com-
bined organic phase was washed with water and brine. The
organic phase was filtered and concentrated under an aspirator
vacuum to give an oil, which was purified by preparative TLC
(hexanes-ethyl acetate, 10:1) to give 1-methoxy-2-decanone
(4) (4.9 mg, 44%) and 1-hydroxy-2-decanone dimethyl acetal
(5) (4.8 mg, 35%). In a separate experiment, the yield (91%)
of methyl acetate was determined by analytical GC (hexane
Sch em e 9
(Z)-(2-acetoxyvinyl)(phenyl)-λ3-iodanes via ester exchange
reaction of the â-acetoxy group. R-λ3-Iodanyl ketones are
highly reactive species and undergo substitution with a
variety of nucleophiles such as halides, thiols, phos-
phines, phosphinic acids, and phosphates, probably via
an SN2 pathway.
1
as the internal standard). Data for 4:35 colorless oil; H NMR
(CDCl3) δ 4.01 (s, 2H), 3.42 (s, 3H), 2.43 (t, J ) 7.3 Hz, 2H),
1.7-1.5 (m, 2H), 1.43-1.12 (m, 10H), 0.88 (t, J ) 5.9 Hz, 3H).
Data for 5: colorless oil; IR (neat) 3486 (br), 1086 cm-1 1H
;
Exp er im en ta l Section
NMR (CDCl3) δ 3.56 (d, J ) 6.1 Hz, 2H), 3.23 (s, 6H), 1.74-
1.48 (m, 2H), 1.4-1.1 (m, 12H), 0.87 (t, J ) 6.5 Hz, 3 H); 13C
NMR (CDCl3) δ 102.1, 61.4, 48.3, 31.9, 31.9, 29.9, 29.5, 29.3,
23.6, 22.7, 14.1; MS m/z (relative intensity) 187 [(M - OMe)+,
100], 105 (34), 101 (19), 71 (11), 57 (20); HRMS m/z calcd for
Gen er a l P r oced u r es. For general experimental details, see
ref 17a. Preparative thin-layer chromatography (TLC) was
carried out on precoated plates of silica gel F-254. Kieselgel
60 (230-400 mesh) was used for flash chromatography. 31P
NMR chemical shifts are referenced to a sample of 85%
H3PO4 (sealed capillary) in CDCl3.
C
11H23O2 [(M - OMe)+] 187.1698, found 187.1700.
Rea ction of 2a w ith Tr ieth yla m in e in Dich lor om eth -
a n e. To a stirred solution of 1-decenyl-λ3-iodane 2a (X ) BF4)
(30 mg, 0.062 mmol) in dichloromethane (1.5 mL) was added
triethylamine (6.9 mg, 0.068 mmol) under nitrogen at room
temperature, and the mixture was stirred for 5 h. After
addition of water, the mixture was extracted with dichlo-
romethane, and the combined organic phase was washed with
water and brine. The organic phase was filtered and concen-
trated under an aspirator vacuum to give an oil, which was
purified by preparative TLC (hexanes-ethyl acetate, 10:1) to
give (2-oxodecyl)triethylammonium tetrafluoroborate (6) (9 mg,
44%), 1-chloro-2-decanone (7a ) (1.7 mg, 14%), and 1-acetoxy-
2-decanone (8)16 (0.5 mg, 4%). Data for 6: white solid; IR (KBr)
1726, 1090 (br) cm-1; 1H NMR (CDCl3) δ 4.41 (s, 2H), 3.58 (q,
J ) 7.3 Hz, 6H), 2.61 (t, J ) 7.3 Hz, 2H), 1.70-1.47 (m, 2H),
1.35-1.15 (m, 10H), 1.33 (t, J ) 7.3 Hz, 9H), 0.88 (t, J ) 6.5
Hz, 3H); HRMS (FAB) m/z calcd for C16H34NO [(M - BF4)+]
256.2640, found 256.2646. Data for 7a :36 colorless oil; 1H NMR
(CDCl3) δ 4.08 (s, 2H), 2.59 (t, J ) 7.4 Hz, 2H), 1.70-1.50 (m,
2H), 1.40-1.17 (m, 10H), 0.88 (t, J ) 6.1 Hz, 3H).
(Z)-(2-Acetoxy-1-decenyl)(phenyl)-λ3-iodane 2a (X ) BF4)
was prepared according to a literature method.17c (Z)-(2-
Acetoxy-5-phenyl-1-pentenyl)(phenyl)-λ3-iodane 2b (X ) BF4)
and (Z)-(2-acetoxy-3,3-dimethyl-1-butenyl)(phenyl)-λ3-iodane
2c (X ) BF4) were prepared from 1-alkynyl(phenyl)-λ3-iodane34
via Michael addition of acetic acid in the presence of sodium
acetate according to a literature procedure.17c
Data for 2b (X ) BF4): white powder; mp 60-62 °C; IR
(KBr) 1762, 1062 cm-1; 1H NMR (CDCl3) δ 7.97 (br d, J ) 8.0
Hz, 2H), 7.60 (br t, J ) 7.4 Hz, 1H), 7.44 (br dd, J ) 8.0, 7.4
Hz, 2H), 7.34-7.06 (m, 5H), 6.65 (s, 1H), 2.64 (t, J ) 7.4 Hz,
2H), 2.60 (t, J ) 7.4 Hz, 2H), 2.24 (s, 3H), 1.82 (quint, J ) 7.4
Hz, 2H); FAB MS m/z 407 [(M - BF4)+]. Anal. Calcd for C19H20
BF4IO2: C, 46.19; H, 4.08. Found: C, 46.23; H, 4.15.
-
Data for 2c (X ) BF4): colorless prisms; mp 89-91 °C
(recrystallized from dichloromethane-diethyl ether); IR (KBr)
1
1769, 1063 (br) cm-1; H NMR (CDCl3) δ 8.02 (br d, J ) 7.5
Hz, 2H), 7.65 (br t, J ) 7.5 Hz, 1H), 7.50 (t, J ) 7.5 Hz, 2H),
6.85 (s, 1H), 2.40 (s, 3H), 1.20 (s, 9H); FAB MS m/z 345 [(M -
BF4)+]. Anal. Calcd for C14H18BF4IO2: C, 38.92; H, 4.20.
Found: C, 38.70; H, 4.18.
Gen er a l P r oced u r e for th e Syn th esis of a n r-Ha lo
Keton e. A Typ ica l Exa m p le (Ta ble 1, En tr y 6): 1-Br om o-
2-d eca n on e (15a ). To a stirred solution of 1-decenyl-λ3-iodane
2a (X ) BF4) (30 mg, 0.062 mmol) and Bu4NBr (24 mg, 0.07
mmol) in methanol (1.5 mL) was added triethylamine (6.9 mg,
Rea ction of 2a w ith Tr ieth yla m in e in Meth a n ol. To a
stirred solution of 1-decenyl-λ3-iodane 2a (X ) BF4) (30 mg,
(33) (a) Koser, G. F.; Chen, K.; Huang, Y.; Summers, C. A. J . Chem.
Soc., Perkin Trans. 1 1994, 1375. (b) Koser, G. F.; Huang, Y.; Chen,
K.; Calvo, K. C. J . Chem. Soc., Perkin Trans. 1 1995, 299.
(34) Ochiai, M.; Kunishima, M.; Sumi, K.; Nagao, Y.; Fujita, E.
Tetrahedron Lett. 1985, 26, 4501.
(35) Collman, J . P.; Winter, S. R.; Clark, D. R. J . Am. Chem. Soc.
1972, 94, 1788.
(36) Rieke, R. D.; Brown, J . D.; Wu, X. Synth. Commun. 1995, 25,
3923.

4412 J . Org. Chem., Vol. 67, No. 13, 2002
Ochiai et al.
0.068 mmol) under nitrogen at room temperature, and the
mixture was stirred for 1 h. After addition of water, methanol
was evaporated under an aspirator vacuum. The mixture was
extracted with diethyl ether, and the combined organic phase
was washed with water and brine. The organic phase was
filtered and concentrated under an aspirator vacuum to give
an oil, which was purified by preparative TLC (hexanes-ethyl
acetate, 10:1) to give 15a (12.1 mg, 84%) as a colorless oil:37
1H NMR (CDCl3) δ 3.89 (s, 2H), 2.65 (t, J ) 7.3 Hz, 2H), 1.72-
1.50 (m, 2H), 1.4-1.15 (m, 10H), 0.88 (t, J ) 6.0 Hz, 3H).
Da ta for 1-Iod o-2-d eca n on e (16a ):38 1H NMR (CDCl3) δ
3.81 (s, 2H), 2.70 (t, J ) 7.7 Hz, 2H), 1.7-1.5 (m, 2H), 1.37-
1.2 (m, 10H), 0.88 (t, J ) 6.0 Hz, 3H).
7.09 (m, 10H), 3.64 (s, 2H), 2.59 (t, J ) 7.4 Hz, 2H), 2.58 (t, J
) 7.4 Hz, 2H), 1.89 (quint, J ) 7.4 Hz, 2H); MS m/z (relative
intensity) 270 (M+, 41), 166 (48), 147 (92), 91 (100); HRMS
m/z calcd for C17H18OS (M+) 270.1078, found 270.1055. Anal.
Calcd for C17H18OS: C, 75.52; H, 6.71. Found: C, 75.18; H,
6.70.
Da ta for 3,3-Dim eth yl-1-p h en ylth io-2-bu ta n on e (17c):
41 colorless oil; IR (CHCl3) 1715 cm-1; 1H NMR (CDCl3) δ 7.45-
7.16 (m, 5H), 3.96 (s, 2H), 1.19 (s, 9H).
Gen er a l P r oced u r e for th e Syn th esis of a P h osp h o-
n iu m Sa lt. A Typ ica l Exa m p le (Ta ble 3, En tr y 1):
(2-Oxod ecyl)tr ip h en ylp h osp h on iu m Tetr a flu or obor a te
(22a ). To a stirred solution of 1-decenyl-λ3-iodane 2a (X ) BF4)
(30 mg, 0.062 mmol) and triphenylphosphine (35 mg, 0.13
mmol) in methanol (2.5 mL) was added triethylamine (6.9 mg,
0.068 mmol) under nitrogen at room temperature, and the
mixture was stirred for 1 h. After addition of water, methanol
was evaporated under an aspirator vacuum. The mixture was
acidified by the addition of 5% aqueous HBF4 solution at 0 °C
and extracted with chloroform, and the combined organic
phase was washed with water. The organic phase was filtered
and concentrated under an aspirator vacuum to give an oil,
which was washed several times with hexane and diethyl ether
by decantation at -78 °C to give 22a (27.5 mg, 89%) as a white
solid: IR (KBr) 1709, 1084 (br) cm-1; 1H NMR (CDCl3) δ 7.85-
Da ta for 1-Br om o-5-p h en yl-2-p en ta n on e (15b): colorless
oil; IR (neat) 1715, 701 cm-1 1H NMR (CDCl3) δ 7.35-7.13
;
(m, 10H), 3.85 (s, 2H), 2.66 (t, J ) 7.4 Hz, 2H), 2.65 (t, J ) 7.4
Hz, 2H), 1.96 (quint, J ) 7.4 Hz, 2H); MS m/z (relative
intensity) 240 (M+, 3), 161 (10), 147 (6), 104 (100), 91 (37).
Rea ction of 2a w ith Tr ieth yla m in e a n d Th iop h en ol
(Ta ble 2, En tr y 1). To a stirred solution of 1-decenyl-λ3-iodane
2a (X ) BF4) (30 mg, 0.062 mmol) and thiophenol (13 mg, 0.12
mmol) in methanol (1.5 mL) was added triethylamine (7.1 mg,
0.07 mmol) under nitrogen at room temperature, and the
mixture was stirred for 1 h. After addition of water, methanol
was evaporated under an aspirator vacuum. The mixture was
extracted with dichloromethane, and the combined organic
phase was washed with water and brine. The organic phase
was filtered and concentrated under an aspirator vacuum to
give an oil, which was purified by preparative TLC (hexanes-
ethyl acetate, 15:1) to give 1-phenylthio-2-decanone (17a ) (5.9
mg, 36%), (Z)-2-acetoxy-1-iodo-1-decene (19) (3.7 mg, 19%), and
2-acetoxy-1-decene (20) (2.4 mg, 20%). Data for 17a :39 colorless
plates; mp 53-54 °C (recrystallized from dichloromethane-
2
7.55 (m, 15H), 4.93 (d, J HP ) 12.2 Hz, 2H), 2.79 (t, J ) 7.1
Hz, 2H), 1.57-1.37 (m, 2H), 1.29-1.08 (m, 10H), 0.85 (t, J )
6.8 Hz, 3H); 13C NMR (CDCl3) δ 202.9 (2J CP ) 7.3 Hz), 134.9,
133.6 (2J CP ) 9.2 Hz), 130.3 (3J CP ) 12.9 Hz), 118.5 (1J CP
)
88.3 Hz), 44.2 (3J CP ) 3.7 Hz), 37.9 (1J CP ) 58.8 Hz), 31.7, 29.3,
29.0, 28.7, 23.2, 22.6, 14.1; 31P NMR (CDCl3) δ 20.6; HRMS
(FAB) m/z calcd for C28H34OP [(M - BF4)+] 417.2347, found
417.2379.
1
hexane); H NMR (CDCl3) δ 7.40-7.15 (m, 5H), 3.67 (s, 2H),
Da t a for (2-Oxo-5-p h en ylp en t yl)t r ip h en ylp h osp h o-
n iu m Tetr a flu or obor a te (22b): pale yellow oil; IR (neat)
1715, 1058 (br) cm-1; 1H NMR (CDCl3) δ 7.84-7.58 (m, 15H),
2.58 (t, J ) 7.4 Hz, 2H), 1.65-1.45 (m, 2H), 1.37-1.17 (m,
10H), 0.87 (t, J ) 6.2 Hz, 3H). Data for 19: colorless oil; IR
(CHCl3) 1755, 1180 cm-1; 1H NMR (CDCl3) δ 5.81 (s, 1H), 2.35
(t, J ) 7.4 Hz, 2H), 2.23 (s, 3H), 1.55-1.38 (m, 2H), 1.36-1.18
(m, 10H), 0.88 (t, J ) 6.1 Hz, 3H); MS m/z (relative intensity)
324 (M+, 7), 282 (28), 197 (12), 184 (21), 155 (47), 95 (45), 81
(52), 43 (100); HRMS m/z calcd for C12H21O2I (M+) 324.0586,
found 324.0587. The (Z)-stereochemistry of 19 was established
by observation of an NOE enhancement between the vinylic
and allylic protons. Data for 20:40 colorless oil; 1H NMR
(CDCl3) δ 4.75-4.68 (m, 2H), 2.20 (t, J ) 7.3 Hz, 2H), 2.14 (s,
3H), 1.55-1.20 (m, 12H), 0.88 (t, J ) 6.1 Hz, 3H).
2
7.30-7.06 (m, 5H), 4.90 (d, J HP ) 11.8 Hz, 2H), 2.86 (t, J )
7.3 Hz, 2H), 2.53 (t, J ) 7.3 Hz, 2H), 1.82 (quint, J ) 7.3 Hz,
2H); FAB MS m/z 423 [(M - BF4)+].
Da ta for (3,3-Dim eth yl-2-oxobu tyl)tr ip h en ylp h osp h o-
n iu m Tetr a flu or obor a te (22c): white powder; mp 162-165
1
°C; IR (KBr) 1698, 1084 (br) cm-1; H NMR (CDCl3) δ 7.85-
2
7.58 (m, 15H), 5.0 (d, J HP ) 12.4 Hz, 2H), 1.18 (s, 9H); FAB
MS m/z 361 [(M - BF4)+]. The salt 22c was contaminated with
a small amount of impurity.
Gen er a l P r oced u r e for th e Syn th esis of a n r-Ketol
P h osp h in a te a n d a n r-P h osp h or yloxy Keton e. A Typ ica l
Exa m p le (Ta ble 3, En tr y 5): 2-Oxod ecyl Dip h en ylp h os-
p h in a te (23a ). To a stirred solution of 1-decenyl-λ3-iodane 2a
(X ) BF4) (30 mg, 0.062 mmol), diphenylphosphinic acid (27
mg, 0.12 mmol), and methanol (4 mg, 0.12 mmol) in dichlo-
romethane (4 mL) was added triethylamine (6.9 mg, 0.068
mmol) under nitrogen at room temperature, and the mixture
was stirred for 17 h. After addition of water, the mixture was
extracted with ethyl acetate, and the combined organic phase
was washed with water. The organic phase was filtered and
concentrated under an aspirator vacuum to give an oil, which
was purified by preparative TLC (hexanes-ethyl acetate, 2:1)
to give 23a (17.1 mg, 78%) as a colorless oil: IR (neat) 1737,
1231, 1132, 1055, 731, 697 cm-1; 1H NMR (CDCl3) δ 7.86 (dd,
Da t a for 1-P h en ylsu lfon yl-2-d eca n on e (18a ): white
solids; IR (KBr) 1718, 1301, 1154 cm-1 1H NMR (CDCl3) δ
;
7.89 (br d, J ) 7.2 Hz, 2H), 7.70 (br t, J ) 7.2 Hz, 1H), 7.58
(br t, J ) 7.2 Hz, 2H), 4.14 (s, 2H), 2.70 (t, J ) 6.8 Hz, 2H),
1.70-1.45 (m, 2H), 1.40-1.15 (m, 10H), 0.89 (t, J ) 6.5 Hz,
3H); MS m/z (relative intensity) 296 (M+, 3), 199 (48), 198 (45),
154 (57), 141 (47), 134 (100), 125 (70), 77 (83); HRMS m/z calcd
for C16H24O3S (M+) 296.1446, found 296.1456.
Gen er a l P r oced u r e for th e Syn th esis of a n r-P h en -
ylth io Keton e. A Typ ica l Exa m p le (Ta ble 2, En tr y 3):
Keton e 17a . To a stirred solution of 1-decenyl-λ3-iodane 2a
(X ) BF4) (30 mg, 0.062 mmol) in THF (6 mL) was added a
0.43 M THF solution of EtOLi (0.145 mL, 0.062 mmol) at -78
°C under argon, and the mixture was stirred for 20 min. After
addition of a solution of thiophenol (21 mg, 0.19 mmol) in THF
(0.2 mL), the mixture was stirred for 1 h at -78 °C. The
reaction mixture was allowed to warm to room temperature
over 8 h, quenched with water, and extracted with dichlo-
romethane. The organic phase was washed with brine, dried
over anhydrous Na2SO4, and concentrated. Preparative TLC
(hexanes-ethyl acetate, 10:1) gave 17a (10.8 mg, 65%).
Da ta for 5-P h en yl-1-p h en ylth io-2-p en ta n on e (17b):
3
J ) 7.4 Hz, J HP ) 12.3 Hz, 4H), 7.63-7.40 (m, 6H), 4.55 (d,
3J HP ) 7.8 Hz, 2H), 2.47 (t, J ) 7.6 Hz, 2H), 1.73-1.50 (m,
2H), 1.35-1.15 (m, 10H), 0.87 (t, J ) 6.0 Hz, 3H); 13C NMR
(CDCl3) δ 205.0 (3J CP ) 6.1 Hz), 132.6 (4J CP ) 3.1 Hz), 131.7
(2J CP ) 10.7 Hz), 130.5 (1J CP ) 137.3 Hz), 128.7 (3J CP ) 12.2
Hz), 67.8 (2J CP ) 6.2 Hz), 38.9, 31.8, 29.3, 29.1, 29.1, 23.2, 22.6,
14.1; 31P NMR (CDCl3) δ -27.3; MS m/z (relative intensity)
372 (M+, 0.4), 231 (100), 201 (34), 92 (16), 77 (13); HRMS m/z
calcd for C22H29O3P (M+) 372.1854, found 372.1838.
1
white powder; IR (KBr) 1707 cm-1; H NMR (CDCl3) δ 7.37-
Da ta for 2-Oxo-5-p h en ylp en tyl Dip h en ylp h osp h in a te
(23b ): colorless oil; IR (CHCl3) 1740, 1240 (br), 1135, 1035
(37) Samuelsson, B.; Stallberg, G. Acta Chem. Scand. 1963, 17, 810.
(38) Antonioletti, R.; D’Auria, M.; Mico, A. D.; Piancatelli, G.; Scettri,
A. Tetrahedron 1983, 39, 1765.
(39) Yoshida, J .; Nakatani, S.; Isoe, S. J . Org. Chem. 1993, 58, 4855.
(40) Hartstock, F. W.; Wayner, D. D. M. Tetrahedron Lett. 1994,
35, 8137.
(41) Matano, Y.; Azuma, N.; Suzuki, H. J . Chem. Soc., Perkin Trans.
1 1994, 1739.

Generation of R-λ3-Iodanyl Ketones
J . Org. Chem., Vol. 67, No. 13, 2002 4413
1
3
cm-1; H NMR (CDCl3) δ 7.84 (br dd, J ) 8.0 Hz, J HP ) 12.6
432 (M+, 0.5), 341 (15), 235 (36), 104 (95), 91 (100), 69 (82), 57
(42); HRMS m/z calcd for C24H33O5P (M+) 432.2066, found
432.2089.
3
Hz, 4H), 7.63-7.40 (m, 6H), 7.35-7.08 (m, 5H), 4.52 (d, J HP
) 7.8 Hz, 2 H), 2.61 (t, J ) 7.3 Hz, 2H), 2.50 (t, J ) 7.3 Hz,
2H), 1.92 (quint, J ) 7.3 Hz, 2H); 31P NMR (CDCl3) δ -27.3;
MS m/z (relative intensity) 378 (M+, 5), 287 (4), 274 (100), 231
(62), 219 (30), 201 (53). 159 (31), 91 (46), 77 (27); HRMS m/z
calcd for C23H23O3P (M+) 378.1385, found 378.1391.
Da ta for Diben zyl 2-Oxo-5-p h en ylp en tyl P h osp h a te
(26b): colorless needles; mp 41.5-43 °C (recrystallized from
dichloromethane-hexane); IR (KBr) 1738, 1260, 1041, 991,
1
741, 669 cm-1; H NMR (CDCl3) δ 7.47-7.10 (m, 15H), 5.11
3
Da ta for 3,3-Dim eth yl-2-oxobu tyl Dip h en ylp h osp h i-
n a te (23c): colorless needles; mp 105-107 °C (recrystallized
from dichloromethane-hexane); IR (KBr) 1736, 1231, 1131,
(dd, J ) 11.9 Hz, J HP ) 8.5 Hz, 2H), 5.06 (dd, J ) 11.9 Hz,
3
3J HP ) 8.5 Hz, 2H), 4.41 (d, J HP ) 9.3 Hz, 2H), 2.59 (t, J )
7.2 Hz, 2H), 2.37 (t, J ) 7.2 Hz, 2H), 1.88 (quint, J ) 7.2 Hz,
2H); MS m/z (relative intensity) 438 (M+, 2), 347 (5), 249 (16),
231 (11), 104 (23), 91 (100). Anal. Calcd for C25H27O5P: C,
68.48; H, 6.21. Found: C, 68.36; H, 6.21.
1050, 1007, 731, 699 cm-1; H NMR (CDCl3) δ 7.97-7.83 (m,
1
3
4H), 7.60-7.40 (m, 6H), 4.86 (d, J HP ) 7.8 Hz, 2H), 1.10 (s,
9H); 31P NMR (CDCl3) δ -27.2; MS m/z (relative intensity)
316 (M+, 7), 259 (68), 231 (100), 201 (71), 149 (58), 77 (47);
HRMS m/z calcd for C18H21O3P (M+) 316.1228, found 316.1204.
Anal. Calcd for C18H21O3P: C, 68.34; H, 6.69. Found: C, 68.34;
H, 6.66.
Da ta for Diben zyl 3,3-Dim eth yl-2-oxobu tyl P h osp h a te
(26c): colorless oil; IR (neat) 1729, 1278, 999, 881, 738 cm-1
;
1H NMR (CDCl3) δ 7.42-7.30 (m, 10H), 5.15 (dd, J ) 11.6 Hz,
3
3J HP ) 8.3 Hz, 2H), 5.10 (dd, J ) 11.6 Hz, J HP ) 8.3 Hz, 2H),
3
4.75 (d, J HP ) 10.3 Hz, 2H), 1.13 (s, 9H); 13C NMR (CDCl3) δ
Da ta for 2-Oxod ecyl Dim eth ylp h osp h in a te (24a ): color-
less oil; IR (neat) 1734, 1307, 1211, 1063, 942, 877 cm-1; H
1
207.6 (3J CP ) 4.5 Hz), 135.8 (3J CP ) 7.6 Hz), 128.6, 128.5, 128.1,
69.6 (2J CP ) 6.1 Hz), 67.0 (2J CP ) 6.1 Hz), 42.7, 26.1; 31P NMR
(CDCl3) δ -0.0; MS m/z (relative intensity) 376 (M+, 2), 285
(13), 179 (48), 104 (61), 91 (100), 57 (32); HRMS m/z calcd for
3
NMR (CDCl3) δ 4.60 (d, J HP ) 10.3 Hz, 2H), 2.43 (t, J ) 7.4
Hz, 2H), 1.70-1.50 (m, 2H), 1.59 (d, 2J HP ) 14.2 Hz, 6H), 1.40-
1.18 (m, 10H), 0.88 (t, J ) 6.3 Hz, 3H); MS m/z (relative
intensity) 248 (M+, 7), 163 (23), 150 (65), 109 (75), 108 (78),
95 (90), 78 (99), 77 (100); HRMS m/z calcd for C12H25O3P (M+)
248.1541, found 248.1534.
C
20H25O5P (M+) 376.1440, found 376.1435.
Da ta for Dibu tyl 2-Oxod ecyl P h osp h a te (27a ): colorless
1
oil; IR (neat) 1740, 1279, 1029 cm-1; H NMR (CDCl3) δ 4.54
(d, 3J HP ) 9.5 Hz, 2H), 4.11 (q, J ) 6.8 Hz, 3J HP ) 6.8 Hz, 4H),
2.48 (t, J ) 7.4 Hz, 2H), 1.73-1.56 (m, 6H), 1.42 (sext, J ) 7.3
Hz, 4H), 1.33-1.20 (m, 10H), 0.94 (t, J ) 7.3 Hz, 6H), 0.88 (t,
J ) 6.6 Hz, 3H); 13C NMR (CDCl3) δ 205.1, 70.4 (2J CP ) 6.1
Hz), 68.0 (2J CP ) 6.1 Hz), 38.6, 32.2 (3J CP ) 7.6 Hz), 31.8, 29.3,
29.1, 29.1, 23.1, 22.6, 18.7, 14.1, 13.6; MS m/z (relative
intensity) 364 (M+, 1), 224 (22), 169 (100), 113 (60), 99 (20),
57 (21); HRMS m/z calcd for C18H37O5P (M+) 364.2379, found
364.2371.
Da ta for 2-Oxo-5-p h en ylp en tyl Dim eth ylp h osp h in a te
(24b): colorless oil; IR (neat) 1734, 1307, 1212, 1070, 941, 876
1
3
cm-1; H NMR (CDCl3) δ 7.36-7.12 (m, 5H), 4.56 (d, J HP
)
10.2 Hz, 2H), 2.65 (t, J ) 7.3 Hz, 2H), 2.44 (t, J ) 7.3 Hz, 2H),
2
1.95 (quint, J ) 7.3 Hz, 2H), 1.57 (d, J HP ) 14.2 Hz, 6H); MS
m/z (relative intensity) 254 (M+, 3), 150 (100), 147 (17), 108
(56), 91 (64), 78 (42), 77 (32); HRMS m/z calcd for C13H19O3P
(M+) 254.1072, found 254.1096.
Da ta for 3,3-Dim eth yl-2-oxobu tyl Dim eth ylp h osp h i-
n a te (24c): colorless oil; IR (neat) 1726, 1308, 1211, 1051,
Da t a for Dib u t yl 2-Oxo-5-p h en ylp en t yl P h osp h a t e
(27b): colorless oil; IR (neat) 1738, 1278, 1029 cm-1; 1H NMR
(CDCl3) δ 7.37-7.10 (m, 5H), 4.52 (d, 3J HP ) 9.3 Hz, 2H), 4.09
1000, 941, 877 cm-1; H NMR (CDCl3) δ 4.87 (d, J HP ) 10.7
1
3
2
Hz, 2H), 1.59 (d, J HP ) 14.2 Hz, 6H), 1.19 (s, 9H); MS m/z
(relative intensity) 192 (M+, 2), 135 (37), 108 (100), 95 (26),
78 (84), 77 (35), 57 (63); HRMS m/z calcd for C8H17O3P (M+)
192.0915, found 192.0922.
3
(q, J ) 7.0 Hz, J HP ) 7.0 Hz, 4H), 2.64 (t, J ) 6.5 Hz, 2H),
2.49 (t, J ) 6.5 Hz, 2H), 1.95 (quint, J ) 6.5 Hz, 2H), 1.67
(quint, J ) 7.0 Hz, 4H), 1.41 (sext, J ) 7.0 Hz, 4H), 0.94 (t, J
) 7.0 Hz, 6H); 13C NMR (CDCl3) δ 204.7 (3J CP ) 6.1 Hz), 141.2,
128.4, 126.1, 70.4 (2J CP ) 6.1 Hz), 68.0 (2J CP ) 6.1 Hz), 37.7,
34.9, 32.2 (3J CP ) 6.1 Hz), 24.4, 18.6, 13.6; 31P NMR (CDCl3) δ
-0.4; MS m/z (relative intensity) 370 (M+, 18), 266 (100), 211
(34), 154 (56), 113 (37), 99 (39), 91 (54); HRMS m/z calcd for
Da ta for Dip h en yl 2-Oxod ecyl P h osp h a te (25a ): color-
less oil; IR (neat) 1739, 1289, 1191, 1026, 957 cm-1; H NMR
1
3
(CDCl3) δ 7.43-7.15 (m, 10H), 4.71 (d, J HP ) 9.0 Hz, 2H),
2.43 (t, J ) 7.5 Hz, 2H), 1.65-1.45 (m, 2H), 1.35-1.15 (m,
10H), 0.88 (t, J ) 6.3 Hz, 3H); 13C NMR (CDCl3) δ 204.1 (3J CP
) 6.0 Hz), 150.3 (2J CP ) 7.6 Hz), 129.9, 125.7, 120.1 (3J CP
)
C
19H31O5P (M+) 370.1909, found 370.1909.
4.5 Hz), 71.5 (2J CP ) 6.0 Hz), 38.6, 31.8, 29.3, 29.2, 29.1, 23.0,
22.6, 14.1; 31P NMR (CDCl3) δ -11.4; MS m/z (relative
intensity) 404 (M+, 20), 311 (100), 264 (17), 175 (89), 166 (58),
141 (18), 77 (40), 57 (62); HRMS m/z calcd for C22H29O5P (M+)
404.1753, found 404.1746.
Da ta for Dibu tyl 3,3-Dim eth yl-2-oxobu tyl P h osp h a te
1
(27c): colorless oil; IR (neat) 1731, 1278, 1030, 998 cm-1; H
3
NMR (CDCl3) δ 4.85 (d, J HP ) 9.9 Hz, 2H), 4.11 (q, J ) 7.3
Hz, 3J HP ) 7.3 Hz, 4H), 1.68 (quint, J ) 7.3 Hz, 4H), 1.42 (sext,
J ) 7.3 Hz, 4H), 1.19 (s, 9H), 0.94 (t, J ) 7.3 Hz, 6H); MS m/z
(relative intensity) 308 (M+, 1),251 (25), 169 (99), 139 (53), 113
(100), 99 (36), 57 (86); HRMS m/z calcd for C14H29O5P (M+)
308.1753, found 308.1751.
Da ta for Diben zyl 2-Oxod ecyl P h osp h a te (26a ): color-
less oil; IR (neat) 1738, 1278, 1016 cm-1; H NMR (CDCl3) δ
1
7.37-7.33 (m, 10H), 5.13 (dd, J ) 11.9 Hz, 3J HP ) 8.9 Hz, 2H),
3
3
5.08 (dd, J ) 11.9 Hz, J HP ) 8.9 Hz, 2H), 4.44 (d, J HP ) 9.2
Hz, 2H), 2.36 (t, J ) 7.4 Hz, 2H), 1.54 (quint, J ) 7.4 Hz, 2H),
1.34-1.18 (m, 10H), 0.88 (t, J ) 6.7 Hz, 3H); 13C NMR (CDCl3)
δ 204.8, 135.6 (3J CP ) 7.3 Hz), 128.7, 128.6, 128.1, 70.4 (2J CP
) 5.4 Hz), 69.7 (2J CP ) 5.4 Hz), 38.5, 31.8, 29.3, 29.1, 23.0,
22.6, 14.1; 31P NMR (CDCl3) δ -0.5; MS m/z (relative intensity)
Su p p or tin g In for m a tion Ava ila ble: 1H or 13C NMR
spectra of new compounds. This material is available free of
charge via the Internat at http://pubs.acs.org.
J O0107711