Convenient, solvent-free method for preparation of [Hydroxy(phosphoryloxy) iodo]arenes

Article abstract of DOI:10.1080/00397910903097229

A convenient, solvent-free method for preparation of [hydroxy(phosphoryloxy)iodo]arenes is reported. (Diacetoxyiodo)benzene or other hypervalent iodine reagents and phosphates are simply blended and ground for several minutes in an agate mortar, giving good yields of [hydroxy(phosphoryloxy)iodo]arenes with excellent purities.

Full text of DOI:10.1080/00397910903097229

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Convenient, Solvent-Free
Method for Preparation of
[Hydroxy(phosphoryloxy)iodo]arenes
Min Zhu a , Cheng Gang Cai a , Wei Ke a & Jing Shao a
a College of Biological and Environmental Sciences, Zhejiang Shuren
University, Hangzhou, China
Version of record first published: 07 Apr 2010.
To cite this article: Min Zhu, Cheng Gang Cai, Wei Ke & Jing Shao (2010): Convenient, Solvent-
Free Method for Preparation of [Hydroxy(phosphoryloxy)iodo]arenes, Synthetic Communications: An
International Journal for Rapid Communication of Synthetic Organic Chemistry, 40:9, 1371-1376
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Synthetic Communications1, 40: 1371–1376, 2010
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397910903097229
CONVENIENT, SOLVENT-FREE METHOD
FOR PREPARATION OF
[HYDROXY(PHOSPHORYLOXY)IODO]ARENES
Min Zhu, Cheng Gang Cai, Wei Ke, and Jing Shao
College of Biological and Environmental Sciences, Zhejiang Shuren
University, Hangzhou, China
A convenient, solvent-free method for preparation of [hydroxy(phosphoryloxy)iodo]arenes
is reported. (Diacetoxyiodo)benzene or other hypervalent iodine reagents and phosphates
are simply blended and ground for several minutes in an agate mortar, giving good yields
of [hydroxy(phosphoryloxy)iodo]arenes with excellent purities.
Keywords: [Hydroxy(phosphoryloxy)iodo]arenas; preparation; solvent-free
The hypervalent iodine reagents, ArIL1L2, with one aryl and two heteroatom ligands
are versatile reagents for the oxidation and functionallization of organic com-
pounds.[1] Because hypervalent iodine reagents are nonmetallic oxidation reagents,
they avoid the issues of toxicity common to many transition metals involved in such
processes. Among them, [hydroxy(tosyloxy)iodo]benzene (Koser’s reagent, HTIB) is
a good reagent for introducing tosylate ligand into ketones, alkenes, and alkenoic
acids to give corresponding a-tosyloxy ketones, vic-ditosyloxyalkanes, and tosyloxy
lactones.[2] It is also a convenient precursor for the preparation of various iodonium
salts.[3] Recently, Yusobov, and Wirth reported a solvent-free method for the syn-
thesis of HTIB and other [hydroxy[(organosulfonyl)oxy]iodo]arenes by the ligand
exchange reaction of (diacetoxyiodo)arenes with the corresponding organosulfonic
acids (Scheme 1).[4]
As a useful reagent analogous to HTIB with iodine(III)-bound phosphate
ligands, [hydroxy((bis(phenyloxy)-phosphoryl)oxy)iodo]benzene was the first reported
member of [hydroxy(phosphoryloxy)iodo]arenes in 1988, which was prepared by the
reaction of (diacetoxyiodo)benzene with diphenyl phosphate in aqueous acetonitrile.[5]
It was found that various ketones and pentenoic acids can be converted directly into
the respective products of a-phosphoryloxylation and phosphoryloxylactonization by
[hydroxy((bis(phenyloxy)phosphoryl)oxy)iodo]benzene. The [hydroxy(phosphoryloxy)
iodo]arenes also reacted easily with terminal alkynes to afford alkynyl phosphates
via the intermediate formation of the respective alkynyl iodonium phosphates,[6]
Received March 12, 2009.
Address correspondence to Min Zhu, Zhejiang Shuren University, College of Biological and
Environmental Sciences, Hangzhou, 310015, China. E-mail: hzzm60@163.com
1371

1372
M. ZHU ET AL.
Scheme 1. A solvent-free method for the synthesis of [hydroxy[(organosulfonyl)oxy]iodo]arenes.
which were difficult to prepare with other methods. Alkynyl phosphates play a
key role in mechanistic and bioorganic chemistry[7]; however, the applications of
[hydroxy(phosphoryloxy)iodo]arenes in organic chemistry are limited in comparison
with [hydroxyl[(organosulfonyl)oxy]iodo]arenes.
To explore their applications in synthesis, we first investigated the simple route
for preparation of [hydroxy(phosphoryloxy)iodo]arenes and got a good result. In
this article, we report a fast, convenient, and solvent-free method for preparation
of [hydroxy(phosphoryloxy)iodo]arenes (Scheme 2).
Initially, we used diphenyl phosphate (2a) as the representative of dialkanyl
phosphate to react with an equivalent of (diacetoxyiodo)benzene (1a); we found
that when they were mixed and ground in an agate mortar for only 5 min, the desired
[hydroxy((bis(phenyloxy)phosphoryl)oxy)iodo]benzene (3a) was afforded by a
ligand exchange reaction in a yield of 87% with excellent purity. According to this
protocol, a serious of experiments were carried out, and the known and unknown
[hydroxy(phosphoryloxy)iodo]arenes (3) were prepared in good yields in short times,
shown in Table 1. All formed [hydroxy(phosphoryloxy)iodo]arenes were character-
1
ized by H NMR, 13C NMR, infrared (IR), mass spectra (MS), and melting points.
It is notable from Table 1 that all the reactions were completed in 10 min and
provided products in good to excellent yields. When (diacetoxyiodo)benzene (1a)
and (diacetoxyiodo)-p-Cl-benzene (1b) were used, the reactions gave products in
excess of 86% yields (entries 1–5). When [bis(trifluoroacetoxy)iodo]benzene (1c)
was used in place of 1a and 1b, the yields of the reactions were somewhat less than
the previous reactions (entries 6–8). We also found that iodosylbenzene (1d) can
react with phosphate; however, the reactions needed longer times, and the yields
were not as good as others (entries 9 and 10). (R)-(–)-1,10-binaphthyl-2,20-diyl
hydrogen phosphate can react with 1a and 1c, giving the new corresponding chiral
hypervalent iodine reagent 3c in excellent yields (entries 3 and 8). Now we are inves-
tigating the applications of 3c in organic chemistry, especially in asymmetry
synthesis, which will be reported in due course.
Scheme 2. A convenient, solvent-free method for preparation of [hydroxy(phosphoryloxy)iodo]arenes.

CONVENIENT PREPARATION OF [HYDROXY(PHOSPHORYLOXY)IODO]ARENES 1373
Table 1. Synthesis of [hydroxy(phosphoryloxy)iodo]arenas
Entry
1
1
2: R
Product 3
Time (min)
5
Yield (%)a
87
PhI(OAc)2
Ph
2a
3a
1a
1a
2
3
4
PhCH2
2b
3b
3c
3d
5
10
5
86
94
98
1a
(R)-(-)-1,10-Binaphthyl-2,20-diyl
2c
2a
p-Cl-C6H4I(OAc)2
1b
5
6
1b
PhI(OCOCF3)2
2b
2a
3e
3a
5
5
94
83
1c
1c
1c
7
8
9
2b
2c
2a
3b
3c
3a
5
10
10
81
85
67
=
PhI
1d
1d
O
10
2b
3b
10
70
aIsolated yield.
In summary, a rapid and convenient method for preparation of [hydroxy
(phosphoryloxy)iodo]arenes is afforded by the simple, solvent-free ligand exchange
reaction in an agate mortar. It is simple and fast, and it affords good to excellent
yields. Furthermore, the range of useful applications of [hydroxy(phosphoryloxy)
iodo]arenes in organic synthesis will be extended.
EXPERIMENTAL
Melting points were determined on a digital melting-point apparatus and
1
were not corrected. H NMR and 13C NMR spectra were measured on a Bruker
Aavance III500-MHz NMR spectrometer, IR spectra were recorded on a FT-170
SX instrument, and MS were determined on an HP5989A mass spectrometer.
Hypervalent iodine reagents were prepared according to literature procedures.[8–11]
All phosphates are commercially available.
General Procedure for Synthesis of [Hydroxy(phosphoryloxy)iodo]-
arenes
(Diacetoxyiodo)benzene 1a (183 mg, 0.568 mmol, 1.0 equiv) and diphenyl
phosphate 2a (143 mg, 0.568 mmol, 1.0 equiv) was gently blended in an agate mortar.
The resulting homogeneous mixture was then ground for 5 min. The formed residue
was washed with diethyl ether (5 mL) and dried under high vacuum to afford
[hydroxy((bis(phenyloxy)-phosphoryl)oxy)iodo]benzene 3a (231 mg, 87% yield).

1374
M. ZHU ET AL.
Selected Data
[Hydroxy((bis(phenyloxy)phosphoryl)oxy)iodo]benzene (3a). Mp 101–
103 ꢀC (lit.[5] 102–105 ꢀC); 1H NMR (500 MHz, CDCl3), d: 7.05–7.09 (m, 6H),
7.20–7.28 (m, 6H), 7.39–7.42 (m, 1H), 7.89 (d, J ¼ 5.5 Hz, 2H); 13C NMR
(125 MHz), d: 120.3, 124.2, 124.3, 130.0, 131.1, 131.8, 132.7, 151.9; IR (KBr),
n=cmꢁ1: 3370, 3058, 1743, 1450, 1295, 1192, 1043.
[Hydroxy[(bis(benzoyloxy)phosphoryl)oxy]iodo]benzene
(3b)[5]. Mp
1
72–73 ꢀC; H NMR (500 MHz, DMSO-d6), d: 4.74 (d, J ¼ 7.0 Hz, 4H), 7.27–4.34
(m, 10H), 7.49–7.52 (m, 2H), 7.56–7.58 (m, 1H), 8.12 (d, J ¼ 7.0 Hz, 2H); 13C
NMR (125 MHz), d: 68.0 (d, J ¼ 5.0 Hz), 124.5, 127.6, 127.9, 128.4, 130.7, 131.2,
132.5, 137.3 (d, J ¼ 6.3 Hz); IR (KBr), n=cmꢁ1: 3369, 3061, 2951, 1454, 1268,
1215, 1024; MS m=z (%): 498 (Mþ, 100).
(R)-[Hydroxy((1,10-binaphthyl-2,20-diylphosphoryl)oxy)iodo]benzene
(3c). Mp 157–160 ꢀC; 1H NMR (500 MHz, CDCl3), d: 7.20 (t, J ¼ 2.5 Hz, 2H),
7.24–7.32 (m, 3H), 7.33–7.36 (m, 4H), 7.43 (t, J ¼ 2.5 Hz, 2H), 7.86 (t, J ¼ 8.0 Hz,
4H), 7.94 (d, J ¼ 7.5 Hz, 2H); 13C NMR (125 MHz), d: 120.5 (d, J ¼ 2.5 Hz), 121.4,
125.7, 126.7, 127.1, 127.5, 128.5, 130.2, 131.3, 131.8, 132.2, 137.5, 146.8 (d,
J ¼ 8.8 Hz); IR (KBr), n=cmꢁ1: 3414, 3068, 1465, 1256, 1231, 1107, 1074; MS, m=z
(%): 568 (Mþ, 100). HRMS: calcd. for C26H18IO5P: 567.9932; found: 567.9921.
[Hydroxy[(bis(phenyloxy)phosphoryl)oxy]iodo]-4-Cl-benzene (3d). Mp
1
95–97 ꢀC; H NMR (500 MHz, CDCl3), d: 7.05–7.11 (m, 6H), 7.16 (d, J ¼ 9.0 Hz,
2H), 7.22–7.26 (m, 4H), 7.74 (d, J ¼ 7.5 Hz, 2H); 13C NMR (125 MHz), d: 120.2
(d, J ¼ 5.0 Hz), 124.9, 129.6, 130.9, 133.9, 138.1, 151.0 (d, J ¼ 7.5 Hz); IR (KBr),
n=cmꢁ1: 3392, 3063, 1489, 1268, 1207, 1109, 1084; MS, m=z (%): 504 (Mþ, 100);
HRMS: calcd. for C18H15ClIO5P: 503.9387; found: 503.9381.
[Hydroxy[(benzoyloxy)phosphoryl)oxy]iodo]-4-Cl-benzene
(3e). Mp
70–72 ꢀC; 1H NMR (500 MHz, CDCl3), d: 4.83 (d, J ¼ 8.0 Hz, 4H), 7.13 (dd,
J ¼ 7.0, 2.0 Hz, 2H), 7.24–7.26 (m, 4H), 7.28–7.32 (m, 6H), 7.84 (d, J ¼ 8.0 Hz,
2H); 13C NMR (125 MHz), d: 68.3 (d, J ¼ 6.3 Hz), 127.6, 128.1, 128.5, 130.8,
133.5, 136.8 (d, J ¼ 7.5 Hz), 137.8, 138.7; IR (KBr), n=cmꢁ1: 3463, 3058, 1422,
1386, 1222, 1100, 1039; EIMS, m=z (%): 532 (Mþ, 100); HRMS: calcd. for
C20H19ClIO5P: 531.9699; found: 531.9679.
ACKNOWLEDGMENT
Financial support from the National Science Foundation of China (Project
20672100) is greatly appreciated.
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