Monoallylation of 1,2-diols by Pd/Sn bimetallic catalysis

Article abstract of DOI:10.1002/chem.201102709

Efficient and mild: The selective monoallylation of 1,2-diols was successfully developed with Pd/Sn bimetallic catalysis in good to excellent yields. This process was carried out with high substrate tolerance under mild conditions (see scheme). The catalyst system achieved the quite high chemoselectivity even in the presence of a 1:1 mixture of the 1,2-diol and mono-ol. Copyright

Full text of DOI:10.1002/chem.201102709

COMMUNICATION
DOI: 10.1002/chem.201102709
Monoallylation of 1,2-Diols by Pd/Sn Bimetallic Catalysis
Masami Kuriyama,[a] Tsubasa Takeichi,[a] Masaaki Ito,[b] Noritsugu Yamasaki,[b]
Ryota Yamamura,[a] Yosuke Demizu,[a] and Osamu Onomura*[a]
Selective transformation of 1,2-diols is highly important in
synthetic organic chemistry and a variety of methods for the
selective monoalkylation of 1,2-diols have been reported,
which required an excess amount of 1,2-diols in most
cases.[1] In the past, many stoichiometric methods have been
developed, such as reductive cleavage of acetals,[2] use of
polymer resins,[3] thallium salts,[4] monosodium salts,[5] silver
oxide,[6] dibutyltin oxide,[7] arylboronic acids,[8] and direct al-
lylation of 1,2-diols through intramolecular dehydrohalo-
the ability of tin salts to selectively activate 1,2-diols has
been already examined.[14,17] A broad range of phosphine li-
gands, palladium catalyst precursors, and tin salts were eval-
uated and selected results were shown in Table 1. First of
Table 1. Optimization of the catalytic system.[a]
ACHTUNGTRENNUNG
genation.[9] On the other hand, only a few catalytic reactions
were reported with limited successful examples using tin di-
chloride,[10] palladium salts,[11] phase-transfer catalysts,[12] and
crown ether.[13] In particular, selective monoallylation of 1,2-
diols is quite important in these types of transformation be-
cause the allyl group can be utilized as a protecting group
and convertible synthetic foothold. However, no successful
monoallylation of 1,2-diols have been reported in catalytic
methods.[2–13]
Entry
Ligand
Pd
Sn
Yield [%][b]
1
2
3
4
5
6
7
8
DPPE[c]
DPPP[d]
DPPB[e]
DPPPent[f]
DPPHex[g]
DPPBz[h]
DPPF[i]
DPPB[e]
DPPB[e]
DPPB[e]
DPPB[e]
DPPB[e]
DPPB[e]
DPPB[e]
DPPB[e]
DPPB[e]
none
Pd
Pd
Pd
Pd
Pd
Pd
Pd
N
Me2SnCl2
Me2SnCl2
Me2SnCl2
Me2SnCl2
Me2SnCl2
Me2SnCl2
Me2SnCl2
Me2SnCl2
Me2SnCl2
Me2SnCl2
Me2SnCl2
Bu2SnCl2
Oc2SnCl2
Ph2SnCl2
Bu2SnO
84
92
94
90
90
93
89
87
73
60
83
82
78
86
80
60
0
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
PdCl2
[Pd
(acac)2][j]
[Pd2dba3][k]
[Pd
(dba)2][k]
(OAc)2
(OAc)2
(OAc)2
(OAc)2
(OAc)2
(OAc)2
Recently, we reported the effective methods for monoacy-
9
ACHTUNGTRENNUNG
lation of 1,2-diols with dimethyltin dichloride[14] or copper-
10
11
12
13
14
15
16
17
18
19
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
(II) salts[15] as catalysts and also developed the selective
AHCTUNGTRENNUNG
Pd
Pd
Pd
Pd
Pd
Pd
ACHTUNGTRENNUNG
monoalkylation of 1,2-diols catalyzed by copper(II) chloride
or arylboronic acids.[16] However, these catalysts gave insuf-
ficient catalytic activity with only a narrow scope of sub-
strates for monoallylation of 1,2-diols. Therefore, we exam-
ined other catalyst systems and found that combined cata-
lysts composed of a transition metal and Lewis acid promot-
ed monoallylation of 1,2-diols effectively. Herein, we de-
scribe the efficient selective monoallylation of 1,2-diols by
Pd/Sn bimetallic catalysis.
Initial studies were aimed at finding effective catalyst sys-
tems for the selective monoallylation of 1,2-diols. Palladium
and tin salts were focused on because palladium salts were
known to be good catalysts in the allylation of mono-ols and
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
R
none
none
Me2SnCl2
Me2SnCl2
A
DPPB[e]
none
none
none
0
0
[a] Reaction conditions: cis-1,2-cyclooctanediol 1a (0.5 mmol), allyl ace-
tate (1.5 mmol), ligand (0.125 mmol), Pd (0.05 mmol), Sn (0.05 mmol),
Cs2CO3 (0.75 mmol), CH2Cl2 (3 mL), room temperature, 22 h. [b] Yield
of the isolated product. [c] 1,2-Bis(diphenylphosphino)ethane. [d] 1,3-
Bis(diphenylphosphino)propane. [e] 1,4-Bis(diphenylphosphino)butane.
[f] 1,5-Bis(diphenylphosphino)pentane. [g] 1,6-Bis(diphenylphosphino)-
hexane. [h] 1,2-Bis(diphenylphosphino)benzene. [i] 1,1’-Bis(diphenylphos-
phino)ferrocene. [j] acac=acetylacetonate. [k] dba=dibenzylideneace-
tone.
[a] Dr. M. Kuriyama, T. Takeichi, R. Yamamura, Dr. Y. Demizu,
Prof. Dr. O. Onomura
all, the investigation of phosphine ligands in the monoallyla-
tion of cis-1,2-cyclooctanediol (1a) with allyl acetate in the
presence of cesium carbonate was conducted in dichlorome-
thane at room temperature (Table 1, entries 1–7). DPPB
was proven to be a superior bidentate phosphine ligand, al-
though most of the phosphine ligands gave excellent results.
A series of palladium sources were screened and palla-
Graduate School of Biomedical Sciences
Nagasaki University
1-14 Bunkyo-machi, Nagasaki (Japan)
Fax : (+81)95-819-2476
E-mail: onomura@nagaski-u.ac.jp
[b] M. Ito, Dr. N. Yamasaki
Daicel Chemical Industries, Ltd.
2-18-1 Konan, Minato-ku, Tokyo (Japan)
AHCTUNGTREGdNNNU ium(II) acetate showed the highest catalytic activity
(Table 1, entries 3 and 8–11). The influence of tin salts was
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/chem.201102709.
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investigated and dimethyltin dichloride was found to be the
most suitable (Table 1, entries 3 and 12–15). On the other
hand, the allylation reaction without tin salts led to a de-
crease in yield (Table 1, entry 16), and the catalytic systems
composed of only palladium(II) acetate, dimethyltin dichlor-
ide with DPPB, or only dimethyltin dichloride did not work
at all (Table 1, entries 17–19). In addition, this catalytic
system showed quite high chemoselectivity (Scheme 1). The
Scheme 2. Allylation using cis-2-(allyloxy)-cyclooctanol or cyclooctanol.
ing the catalytic systems and chemoselectivity suggested that
palladium(II) acetate with DPPB was fundamental for the
induction of allylation and dimethyltin dichloride was effec-
tive for the selective recognition and reactivity enhancement
of diols by bidentate complexation,[18] which could not be
achieved effectively in the case of cis-2-(allyloxy)-cycloocta-
nol 2a.
Scheme 1. Allylation using cis-1,2-cyclooctanediol and cyclooctanol.
Investigation of various symmetric diols in the allylation
with the Pd/Sn bimetallic catalyst using allyl acetate was
conducted (Table 2). Although cis-1,2-cycloheptanediol (1b)
and cis-1,2-cyclohexanediol (1c) led to excellent yields
(Table 2, entries 1 and 2), the allylation of cis-1,2-cyclopen-
tanediol (1d) gave the product 2d in 74% yield (Table 2,
entry 3). The trans-isomer 1e was also a good substrate in
this catalytic monoallylation, affording the product in 99%
catalytic allylation with a 1:1 mixture of cis-1,2-cyclooctane-
diol and cyclooctanol was conducted to give the monoal-
lyalted product and unreacted cyclooctanol in 75 and 99%
yields, respectively. The mono-ols such as cis-2-(allyloxy)-cy-
clooctanol 2a and cyclooctanol did not react at all under the
same reaction conditions (Scheme 2). These results regard-
Table 2. Scope of diols.[a]
Entry
Substrate 1
Product 2
Yield
[%][b]
Entry
Substrate 1
Product 2
Yield
[%][b]
1
99[d]
90[d]
74[d]
99[d]
97
9
98
2
10
11
12
13[c]
14
15
99[d]
87
3
4
98
5
45
6
88
91
7[c]
99[d]
77
8
97
16
0
[a] Reaction conditions: diol 1 (0.5 mmol), allyl acetate (1.5 mmol), DPPB (0.125 mmol), Pd
CATHNUGTREN(NUNG OAc)2 (0.05 mmol), Me2SnCl2 (0.05 mmol), Cs2CO3
(0.75 mmol), CH2Cl2 (3 mL), room temperature, 22 h. [b] Yield of the isolated product. [c] Allyl acetate (2.0 equiv). [d] Yields were determined by GC.
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Chem. Eur. J. 2012, 18, 2477 – 2480

Monoallylation of 1,2-Diols
COMMUNICATION
yield (Table 2, entry 4). The reaction with cyclic cis-1,2-diols
containing p bonds proceeded with no side product to give
excellent results (Table 2, entries 5 and 6). The heterocyclic
cis-3,4-diols containing oxygen, sulfur, and nitrogen were ex-
amined. This type of heterocyclic substrate did not decrease
the reaction rate (Table 2, entries 7–9). The allylation of ali-
phatic linear meso-1,2-diols 1k proceeded efficiently as ex-
pected, affording the quantitative yield (Table 2, entry 10).
Although the linear meso-1,2-diols with aromatic rings were
easily converted to the desired monoallylated compounds
(Table 2, entries 11 and 12), the substrate with ester groups
gave a moderate yield (Table 2, entry 13). The threo-hydro-
benzoin 1o also reacted with ally acetate smoothly with
91% yield (Table 2, entry 14). Although the 1,3-diol 1p was
suitable for this allylation method (Table 2, entry 15), the al-
lyaltion reaction of 1,4-diol 1q did not take place at all
(Table 2, entry 16).
cused on the development of an asymmetric version in our
research group.
Experimental Section
Representative procedure for selective monoallylation of 1,2-diols
(Table 1, entry 3): Under an atmosphere of air, a round-bottomed flask
was charged with palladium(II) acetate (11.2 mg, 0.05 mmol), 1,4-bis(di-
phenylphosphino)butane (53.3 mg, 0.125 mmol), dimethyltin dichloride
(11.0 mg, 0.05 mmol), cis-1,2-cyclooctanediol 1a (72 mg, 0.5 mmol), and
cesium carbonate (245 mg, 0.75 mmol). Then, dichloromethane (3 mL)
was added followed by allyl acetate (150 mg, 1.5 mmol) and the mixture
was stirred at room temperature for 22 h. After this time water was
added and the resulting mixture was extracted with ethyl acetate and the
combined organic layers were dried with anhydrous magnesium sulfate.
After filtration, the volatile components were removed with a rotary
evaporator. Purification of the crude product through silica gel column
chromatography (hexane/ethyl acetate=10:1) gave 86 mg (0.47 mmol,
94% yield) of the allylated product 2a.
On the other hand, unsymmetrical linear substrates that
contain primary and secondary alcohols in one molecule
were examined under the same reaction conditions
(Scheme 3). Only the primary alcohol moiety in diols 1r and
Acknowledgements
This research was supported by the presidentꢁs discretion fund of Nagasa-
ki University and a Grant-in-Aid for Young Scientists (B) from The
Japan Society for the Promotion of Science (JSPS).
Keywords: allylation
palladium · tin
·
bimetallic catalysis
·
diols
·
[1] a) G. H. Lee, E. B. Choi, E. Lee, C. S. Pak, J. Org. Chem. 1994, 59,
1428–1443; b) E. N. Guidry, S. J. Cantrill, J. F. Stoddart, R. H.
Grubbs, Org. Lett. 2005, 7, 2129–2132.
[2] a) S. Takano, M. Akiyama, S. Sato, K. Ogasawara, Chem. Lett. 1983,
1593–1596; b) T. Mikami, H. Asano, O. Mitsunobu, Chem. Lett.
1987, 2033–2036; c) M. Takasu, Y. Naruse, H. Yamamoto, Tetrahe-
dron Lett. 1988, 29, 1947–1950; d) D. H. R. Barton, J. Zhu, Tetrahe-
dron 1992, 48, 8337–8346.
[3] a) C. C. Leznoff, Acc. Chem. Res. 1978, 11, 327–333; b) T. Nishigu-
chi, K. Kawamine, T. Ohtsuka, J. Chem. Soc. Perkin Trans. 1 1992,
153–156.
Scheme 3. Allylation of unsymmetrical substrates.
[4] H.-O. Kalinowski, G. Crass, D. Seebach, Chem. Ber. 1981, 114, 477–
487.
[5] P. G. McDougal, J. G. Rico, Y.-I. Oh, B. D. Condon, J. Org. Chem.
1986, 51, 3388–3390.
[6] A. Bouzide, G. Sauve, Tetrahedron Lett. 1997, 38, 5945–5948.
[7] a) N. Nagashima, M. Ohno, Chem. Pharm. Bull. 1991, 39, 1972–
1982; b) J. Aubꢂ, C. J. Mossman, S. Dickey, Tetrahedron 1992, 48,
9819–9826; c) F. Scheufler, M. E. Maier, Synlett 2001, 1221–1224;
d) K. S. Kim, Y. J. Lee, J. H. Kim, D. K. Sung, Chem. Commun.
2002, 1116–1117; e) S. Hanessian, G. Huang, C. Chenel, R. Machaa-
lani, O. Loiseleur, J. Org. Chem. 2005, 70, 6721–6734; f) B. Schmidt,
S. Nave, Adv. Synth. Catal. 2007, 349, 215–230.
1s was allylated and the products 2r and 2s were obtained
in 98 and 87% yields, respectively.[19,20] The allylated glycer-
ol derivative 2s is known as a useful intermediate for biolog-
ically active agents.[21] This reaction system was also effec-
tive for triol 1t, leading to an acceptable yield without any
other allylated compounds.[22]
In summary, we have developed the efficient selective
monoallylation of 1,2-diols with Pd/Sn bimetallic catalysis.
This process was successfully applied to various diols, such
as cyclic 1,2-diols containing p bonds, heterocyclic 1,2-diols,
and an aliphatic 1,3-diol, as well as aliphatic cyclic and
linear 1,2-diols. In addition, the catalyst system achieved
high chemoselectivity even in the presence of a 1:1 mixture
of cis-1,2-cyclooctanediol and cyclooctanol. This selective al-
lylation could be useful for synthetic studies because it was
carried out under mild conditions. Further efforts will be fo-
[8] K. Oshima, E. Kitazono, Y. Aoyama, Tetrahedron Lett. 1997, 38,
5001–5004.
[9] S. C. Jha, N. N. Joshi, J. Org. Chem. 2002, 67, 3897–3899.
[10] a) S. Petursson, J. M. Webber, Carbohydr. Res. 1982, 103, 41–52;
b) S. Petursson, Carbohydr. Res. 2003, 338, 963–968.
[11] a) R. Lakhmiri, P. Lhoste, D. Sinou, Tetrahedron Lett. 1989, 30,
4669–4672; b) Y. Bikard, R. Mezaache, J.-M. Weibel, A. Benkouid-
er, C. Sirlin, P. Pale, Tetrahedron 2008, 64, 10224–10232.
[12] J. De La Zerda, G. Barak, Y. Sasson, Tetrahedron 1989, 45, 1533–
1536.
Chem. Eur. J. 2012, 18, 2477 – 2480
ꢀ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
2479

O. Onomura et al.
[13] M. Bessodes, C. Boukarim, Synlett 1996, 1119–1120.
G. Mogami, H. Harasawa, Y. Matsumura, O. Onomura, Chem. Eur.
J. 2009, 15, 5364–5370.
[14] a) T. Maki, F. Iwasaki, Y. Matsumura, Tetrahedron Lett. 1998, 39,
5601–5604; b) F. Iwasaki, T. Maki, W. Nakashima, O. Onomura, Y.
Matsumura, Org. Lett. 1999, 1, 969–972; c) F. Iwasaki, T. Maki, O.
Onomura, W. Nakashima, Y. Matsumura, J. Org. Chem. 2000, 65,
996–1002; d) Y. Demizu, Y. Kubo, H. Miyoshi, T. Maki, Y. Matsu-
mura, N. Moriyama, O. Onomura, Org. Lett. 2008, 10, 5075–5077.
[15] a) Y. Matsumura, T. Maki, S. Murakami, O. Onomura, J. Am. Chem.
Soc. 2003, 125, 2052–2053; b) Y. Matsumura, T. Maki, K. Tsuruma-
ki, O. Onomura, Tetrahedron Lett. 2004, 45, 9131–9134; c) K. Mat-
sumoto, M. Mitsuda, N. Ushijima, Y. Demizu, O. Onomura, Y. Mat-
sumura, Tetrahedron Lett. 2006, 47, 8453–8456; d) Y. Demizu, K.
Matsumoto, O. Onomura, Y. Matsumura, Tetrahedron Lett. 2007, 48,
7605–7609; e) M. Kuriyama, S. Tanigawa, Y. Kubo, Y. Demizu, O.
Onomura, Tetrahedron: Asymmetry 2010, 21, 1370–1373.
[19] The 1H and 13C NMR data of 2r basically corresponded to those of
1-(allyloxy)-hexan-2-ol: J. M. Ready, E. N. Jacobsen, J. Am. Chem.
Soc. 2001, 123, 2687–2688.
[20] Primary hydroxyl groups are transformed more readily due to less
steric hindrance: M. Ikejiri, K. Miyashita, T. Tsunemi, T. Imanishi,
Tetrahedron Lett. 2004, 45, 1243–1246 and references cited therein.
[21] a) A. Stadelmaier, S. Morath, T. Hartung, R. R. Schmidt Angew.
Chem. 2003, 115, 945–949; Angew. Chem. Int. Ed. 2003, 42, 916–
920; Angew. Chem. Int. Ed. 2003, 42, 916–920; b) J. Shin, D. H.
Thompson, J. Org. Chem. 2003, 68, 6760–6766; c) W. F. J. Hogen-
dorf, L. J. van den Bos, H. S. Overkleeft, J. D. C. Codꢂe, G. A. van
der Marel, Bioorg. Med. Chem. 2010, 18, 3668–3678.
[22] To determine the structure of 2t, it was converted into 1-(allyloxy)-
hexan-2-ol. See the Supporting Information for details.
[16] T. Maki, N. Ushijima, Y. Mtsumura, O. Onomura, Tetrahedron Lett.
2009, 50, 1466–1468.
[17] Reviews: a) J. Muzart, Tetrahedron 2005, 61, 5955–6008; b) J.
Muzart, J. Mol. Catal. A 2010, 319, 1–29.
[18] Tin salts proved to be effective for selective reactivity enhancement
of diols by measurement of oxidation potentials: T. Maki, S. Iikawa,
Received: August 30, 2011
Published online: January 27, 2012
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