Preparation of cyclopropanediol: Novel [2 + 1] cycloaddition reaction of bis(iodozincio)methane with 1,2-diketones [27]

Full text of DOI:10.1021/ja003360v

J. Am. Chem. Soc. 2000, 122, 12047-12048
12047
Preparation of Cyclopropanediol: Novel [2 + 1]
Cycloaddition Reaction of Bis(iodozincio)methane
with 1,2-Diketones
Scheme 1
Katsumi Ukai, Koichiro Oshima, and Seijiro Matsubara*
Table 1. [2 + 1] Reaction of Bis(iodozincio)Methane with
1
,2-Dicarbonyl Compoundsa
Department of Material Chemistry
Graduate School of Engineering, Kyoto UniVersity
Yoshida, Sakyo, Kyoto 606-8501, Japan
ReceiVed September 13, 2000
yield
gem-Dizinc reagents which possess a couple of nucleophilic
b
entry
R1
R2
El+
of 3 (%)
sites on a carbon have been used for a variety of characteristic
1
transformations; the reagents can form two C-C bonds on one
1
2
3
4
5
6
7
8
9
Ph
Ph
Ph
Ph
CH3CH2
Ph
Ph
Me3SiCl
78
80
98
97
59
3b
3c
3d
3e
3f
3g
3h
3i
+
Me
Me
Me
H3O
carbon atom. The zinc reagents are relatively stable and have
moderate reactivity compared to corresponding other dimetal
compounds such as dilithium and dimagnesium compounds.2
These features point to the possibility of the selective reaction
combining an appropriate mediator, activator, or catalyst. We have
reported the selective alkylidenation of carbonyl compounds with
Ac2O
Me3SiCl
CH3CH2 Ac2O
c
H
Ac2O
58
H O+
20d
-C(Me) -(CH ) -C(Me) -
2
2 3
2
3
+
d,e
-(CH2)6-
-(CH2)6-
H3O
69
3
gem-dizinc compounds mediated by titanium(II) chloride and the
Ac2O
66
3j
sequential coupling with a pair of organic halides catalyzed with
a
+
1
,2-diketone (2, 1.0 mmol), gem-dizinc 1 (1.2 mmol) and El (2.4
a palladium complex.4
b
mmol) were used. Isolated yields. In each entry, only cis-isomer was
Activation by a ligand as well as a solvent was also examined,
and it was shown that coordination of a heteroatom to zinc
formed diastereoselectively. c The methylenated product (1-phenyl-2-
propenone) was also isolated in 17% yield. 1-phenyl-2-propenol was
isolated in 17% yield. d The product was converted into cyclic1,3-
diketone during the exposure to air. 3h was converted into 4,4,8,8-
tetramethyl-1,3-cyclooctadienone in 55% yield after exposing in air
for 3 days. 3i was converted into 1,3-cyclononadione in 44% yield
after exposing in air for 3 days. e The methylenated product (2-
methylenecyclooctanone) was isolated in 10% yield.
5
enhanced the nucleophilicity of bis(iodozincio)methane (1). In
the case of a heteroatom-containing substrate, such as R-alkoxy
ketone, the same type of activation can be expected. For example,
in the reaction of organomagnesium reagents, the key to the well-
6
known Cram chelation control with R-alkoxy ketones is con-
sidered to be an activation of the reagent with coordination of
7
the R-substituted heteroatom to magnesium. A reaction of a
9
a derivative of [2 + 1] cycloaddition product 3a. Here we wish
to report the efficient [2 + 1] cycloaddition reactions.
Benzil (2a) was treated with bis(iodozincio)methane (1) at 25
C in THF for 0.5 h. Acetic anhydride was added to the reaction
simple ketone with 1 resulted in the complete recovery of the
1
0
3
starting substrate, and thus we tried to react the dizinc 1 with an
R-heteroatom-substituted ketone. 1,2-Diketone, which has a Lewis
basic heteroatom at the R-position of a carbonyl group, seems to
be an attractive substrate for the reaction with bis(iodozincio)-
°
mixture, and the whole was stirred for another 30 min at 25 °C.
After aqueous workup followed by purification with silica gel
column chromatography, cis-1,2-diphenylcyclopropanediol diac-
etate was obtained in 69% yield diastereoselectively. An X-ray
analysis confirmed the structure and stereochemistry. Other
examples are summarized in Table 1.
Instead of acylation, an addition of chlorotrimethylsilane to
the [2 + 1] reaction mixture gave a silyl ether (entries 1 and 4).
Depending on the substrate, the formed 1,2-cyclopropanediol
possesses reasonable stability that enable isolation by a silica gel
column chromatography (entry 2), but in some cases the product
was isomerized into 1,3-diketone gradually under exposure to air
during the isolation procedure (entries 7 and 8). In all cases, the
8
methane (1). The coordination or chelation will activate the zinc
reagent and permit a nucleophilic reaction with the carbonyl. The
reaction may result in the methylenation of a single carbonyl group
under activation with the neighboring carbonyl group to afford
an enone. We examined the reaction of 1 with benzil (2a) as
shown in Scheme 1. Contrary to our expectation, the product was
1
1
*
To whom correspondence should be addressed. Fax +81(75)7534863.
E-mail: matsubar@mc.kyoto-u.ac.jp.
1) (a) Knochel, P.; Normant, J.-F. Tetrahedron Lett. 1986, 27, 4427 and
(
4
431. (b) Marek, I.; Normant, J.-F. Chem. ReV. 1996, 96, 3241. (c) Matsubara,
S. J. Org. Synth. Soc. Jpn. 2000, 58, 118. (d) Marek, I.; Normant, J.-F. In
Organozinc Reagents. A Practical Approach; Knochel, P., Jones, P. Eds.;
Oxford Uninersity Press: 1999; 119.
[
2 + 1] reaction proceeded stereoselectively to give cis-diol
(2) Knochel, P. In Handbook of Grignard Reagents; Silverman, G. S.,
Rakita, P. E., Eds.; Marcel Dekker Inc.: New York, 1996; p 633. Berttini,
F.; Gasselli, P.; Zubiani, G.; Cainelli, G. Tetrahedron 1970, 26, 1281. van de
Heisteeg, B. J. J.; Schat, M. A.; Tinga, G.; Akkerman, O. S.; Bickelhaupt, F.
Tetrahedron Lett. 1986, 27, 6123. Kaiser, E. M.; Solter, L. E.; Schwarz, R.
A.; Beard, R. D.; Hauser, C. R. J. Am. Chem. Soc. 1971, 93, 4237.
(9) Davis, B. R.; Hinds, M. G.; Ting, P. P. C. Aust. J. Chem. 1992, 45,
865; Yoshioka, M.; Mitazoe, S.; Hasegawa, T. J. Chem. Soc., Perkin Trans
I 1993, 2781; Hasegawa, E.; Katagi, H.; Nakagawa, D.; Horagichi, T.
Tetrahedron Lett. 1995, 36, 6915.
(
3) Matsubara, S.; Mizuno, T.; Otake, T.; Kobata, M.; Utimoto, K.; Takai,
(10) Zeller, K.-P.; Gugel, H. In Houben-Weyl: Methoden der Organischem
Chemie; Regitz, M., Ed.; Georg Thieme Verlag: Stuttgart, 1989; Band EXIXb,
p 195. Charette, A. B. In Organozinc Reagents. A Practical Approach;
Knochel, P., Jones, P., Eds.; Oxford Uninersity Press: 1999; p 263.
(11) For the X-ray diffraction, a crystal was mounted on a glass fiber coated
with epoxy resin. Measurements were made on a Rigaku Mercury charge-
coupled device (CCD) system with graphite monochromated Mo KR radiation.
Crystal data: 3a, M ) 310.35, monoclinic, a ) 43.816(9) Å, b ) 5.922(2) Å,
K. Synlett 1998, 1369; Matsubara, S.; Ukai, K.; Mizuno, T.; Utimoto, K. Chem.
Lett. 1999, 825.
(4) Utimoto, K.; Toda, N.; Mizuno, T.; Kobata, M.; Matsubara, S. Angew.
Chem., Int. Ed. Engl. 1997, 36, 2804. Matsubara, S.; Yoshino, H.; Utimoto,
K.; Oshima, K. Synlett 2000, 495.
(
(
(
5) Matsubara, S.; Yamamoto, Y.; Utimoto, K. Synlett 1998, 1471.
6) Cram, D. J.; Kopecky, K. R.; J. Am. Chem. Soc. 1959, 81, 1778.
7) Chen X.; Hortelano, E. R.; Eliel, E. L.; Frye, S. V. J. Am. Chem. Soc.
3
3
c ) 38.178(8) Å, â ) 100.53°, V ) 9739(3) Å , Z ) 24, Fcacl ) 1.270 g/cm ,
-1
1
992, 114, 1778; Utimoto, K.; Nakamura, A.; Matsubara, S. J. Am. Chem.
Soc. 1990, 112, 8189.
8) Eisch reported that the reaction of [(phenylsulfonyl)methylene]dilithium
λ (Mo KR) ) 0.71069 Å, F(000) ) 3936.00, µ (Mo KR) ) 0.88 cm , T )
296 K, 2θmax ) 54.0°, R ) 0.130 for 4583 reflections (I > 2σ(I)). 3j, M )
240.30, orthorhombic, a ) 12.965(1) Å, b ) 17.957(2) Å, c ) 5.691(1) Å, V
(
3
3
with benzil gave 1,3-diphenyl-1,3-propanedione in 40% yield and benzoin in
) 1308.1(6) Å , Z ) 4, Fcacl ) 1.220 g/cm , λ (Mo KR) ) 0.71069 Å, F(000)
-1
2
3
7% yield. See, Eisch, J. J.; Dua, S. K.; Behrooz, M. J. Org. Chem. 1985, 50,
) 520.00, µ (Mo KR) ) 0.89 cm , T ) 296 K, 2θmax ) 54.2°, R ) 0.054
for 1164 reflections (I > 2σ(I)).
674.
1
0.1021/ja003360v CCC: $19.00 © 2000 American Chemical Society
Published on Web 11/16/2000

12048 J. Am. Chem. Soc., Vol. 122, No. 48, 2000
Communications to the Editor
Scheme 2
Although a few synthetic transformations of cyclopropanediol
were already reported,12 we tried to perform a ring-opening
reaction using a Lewis acid having oxidizing ability. As shown
in Scheme 3, trimethylsilyl ether of cyclopentanediol 3b,e was
converted into 1,3-diketone in reasonable yields under the
influence of iron(III) chloride in THF.13 The net transformation
can be recognized as methylene insertion to 1,2-diketone com-
pounds.8
Scheme 3
Acknowledgment. We gratefully thank Dr. Mitsuru Kondo and
Professor Susumu Kitagawa (Department of Synthetic Chemistry and
Biological Chemistry, Graduate School of Engineering, Kyoto University)
for all X-ray measurements. This work was supported by a Grant-in-Aid
from The Ministry of Education, Science, Sports, and Culture.
derivatives. In entry 6, R-keto aldehyde and bis(iodozincio)-
methane also gave cyclopropanediol although methylenation of
aldehyde proceeded to some extent.3
Supporting Information Available: Experimental details for the
preparation of 1, 3a-j, and 7a, and H NMR and C NMR data of 1,
a-j, and 7a; ORTEP and CIF file of 3a, j. This material is available
1
13
3
We propose that the following explanation is plausible for the
free of charge via Internet at http://pubs.acs.org.
[2 + 1] cycloaddition. As shown in Scheme 2, 1,2-diketone would
coodinate with dizinc 1 in s-cis form (4). Coordination of one
zinc atom to one carbonyl which enhances the nucleophilicity of
another Zn-C bond (5), results in zinc methylation to form the
intermediate 6. In the intermediate 6, the Zn-C bond is activated
by the coordination of the R′-alkoxy group and leads to [2 + 1]
cyclization to form 3.
JA003360V
(12) Takeda, K.; Nakatani, J.; Nakamura, H.; Sako, K.; Yoshii, E.;
Yamaguchi, K. Synlett 1993, 841. Davis, B. R.; Rewcastle, G. W.; Woodgate,
P. D. J. Chem. Soc., Perkin Trans. 1 1979, 2820.
(
13) The following results transforming 3e into 7a were also obtained using
the other metal salts: TiCl (68%), SnCl (32%).
4
4