L.-X. Shao, J. Li, B.-Y. Wang, M. Shi
FULL PAPER
National Natural Science Foundation of China (20872162,
20672127, 20821002, 20732008, and 20702013) is greatly acknowl-
edged. We also thank Mr. Jie Sun and Mr. Hu-Ping Zhu for per-
forming X-ray diffraction.
Experimental Section
General Procedure for the Pd-Catalyzed Reactions of Methylene-
cyclopropylcarbinols (Z)-1 in the Presence of Acetic Acid: Under an
argon atmosphere, a mixture of methylenecyclopropylcarbinols 1a
(0.4 mmol), Pd(PPh3)4 (0.02 mmol), AcOH (5.0 mmol), AsPh3
(0.16 mmol), and toluene (2.0 mL) was stirred at 80 °C for 6 h.
Then, the solvent was removed under reduced pressure, and the
residue was purified by a silica gel column chromatography to give
product 4a as a colorless liquid.
[1] For the synthesis of MCPs, see: a) A. Brandi, A. Goti, Chem.
Rev. 1998, 98, 589–636; b) A. de Meijere (Ed.), Carbocyclic
Three-Membered Ring Compounds (Houben-Weyl), Thieme,
Stuttgart, 1996, vol. E17a–c.
[2] For recent reviews, see: a) I. Nakamura, Y. Yamamoto, Adv.
Synth. Catal. 2002, 344, 111–129; b) A. Brandi, S. Cicchi, A.
Cordero, A. Goti, Chem. Rev. 2003, 103, 1213–1270; c) M. Ru-
bin, M. Rubina, V. Gevorgyan, Chem. Rev. 2007, 107, 3117–
3179.
[3] For a review of Lewis acid or Brønsted acid catalyzed transfor-
mations of MCPs, see: a) L.-X. Shao, M. Shi, Curr. Org. Chem.
2007, 11, 1135–1153; for Lewis acid catalyzed cycloaddition
reactions of MCPs developed by this group, see: b) M. Shi, L.-
X. Shao, B. Xu, Org. Lett. 2003, 5, 579–582; c) L.-X. Shao, M.
Shi, Adv. Synth. Catal. 2003, 345, 963–966; d) M. Shi, B. Xu,
Org. Lett. 2003, 5, 1415–1418; e) M. Shi, B. Xu, J.-W. Huang,
Org. Lett. 2004, 6, 1175–1178; f) L.-X. Shao, B. Xu, J.-W. Hu-
ang, M. Shi, Chem. Eur. J. 2006, 12, 510–517; for some other
recent selected papers, see: g) L. Yu, J.-D. Meng, L. Xia, R.
Guo, J. Org. Chem. 2009, 74, 5087–5089; h) X. Huang, M.-Z.
Miao, J. Org. Chem. 2008, 73, 6884–6887; i) X. Huang, Y.-W.
Yang, Org. Lett. 2007, 9, 1667–1670.
[4] For the Pd-catalyzed transformations of MCPs developed by
this group, see: a) M. Shi, L.-P. Liu, J. Tang, Org. Lett. 2006,
8, 4043–4046; b) M. Shi, L.-P. Liu, J. Tang, J. Am. Chem. Soc.
2006, 128, 7430–7431; c) M. Shi, Y. Chen, B. Xu, Org. Lett.
2003, 5, 1225–1228; d) M. Shi, B.-Y. Wang, J.-W. Huang, J.
Org. Chem. 2005, 70, 5606–5610.
General Procedure for the Pd-Catalyzed Isomerization of Methyl-
enecyclopropylcarbinols (E)-1 To Give Pent-4-Enal in the Absence of
Acetic Acid: Under an argon atmosphere, a mixture of methylene-
cyclopropylcarbinol 1g (0.25 mmol), freshly prepared Pd(PPh3)4
(0.025 mmol), and benzene (1.0 mL) was stirred under reflux for
about 8 h. Then, the solvent was removed under reduced pressure,
and the residue was purified by a silica gel column chromatography
to give product 3a as a yellow liquid.
General Procedure for the Preparation of Methylenecycloprop-
anecarbaldehydes 5: To a solution of oxalyl chloride (750 µL,
8.5 mmol) in CH2Cl2 (10.0 mL) at –60 °C was successively added a
solution of DMSO (1.25 mL, 17.5 mmol) in CH2Cl2 (2.0 mL), and
after the reaction mixture was stirred for about 2 min, a solution
of methylenecyclopropylcarbinol 1a (800 mg, 5.0 mmol) in CH2Cl2
(3.0 mL) was added within 5 min. Stirring was continued for 30 min
and triethylamine (3.5 mL, 25.0 mmol) was added into the reaction
solution dropwise. The reaction mixture was warmed to room tem-
perature. An aqueous solution of 1.0 hydrochloric acid (27.5 mL)
saturated with sodium chloride was added into the reaction mix-
ture, and the aqueous layer was extracted with CH2Cl2 (2ϫ15 mL).
The organic layers were combined and dried with anhydrous mag-
nesium sulfate. Then, the solvent was removed under reduced pres-
sure, and the residue was purified by a silica gel column chromatog-
raphy to give product 5a as a yellow liquid.
[5] a) K. Okuma, Y. Tanaka, K. Yoshihira, A. Ezaki, G. Koda, H.
Ohta, K. Hara, S. Kashimura, J. Org. Chem. 1993, 58, 5915–
5917; b) M. Lautens, P. H. M. Delanghe, J. Org. Chem. 1993,
58, 5037–5039; c) M. L. Corre, A. Hercouet, B. Bessieres, J.
Org. Chem. 1994, 59, 5483–5484.
[6] a) B.-Y. Wang, J.-W. Huang, L.-P. Liu, M. Shi, Synlett 2005,
421–424; b) G.-Q. Tian, M. Shi, Tetrahedron Lett. 2006, 47,
8059–8062; c) G.-Q. Tian, M. Shi, Org. Lett. 2007, 9, 2405–
2408; d) L.-X. Shao, Y.-X. Li, M. Shi, Chem. Eur. J. 2007, 13,
862–869; e) G.-Q. Tian, M. Shi, Org. Lett. 2007, 9, 4917–4920;
f) M.-H. Qi, L.-X. Shao, M. Shi, Synthesis 2007, 3567–3573;
g) G.-Q. Tian, J. Li, M. Shi, J. Org. Chem. 2008, 73, 673–677;
h) L.-X. Shao, M.-H. Qi, M. Shi, Tetrahedron Lett. 2008, 49,
165–168.
[7] M. Shi, B.-Y. Wang, L.-X. Shao, Synlett 2007, 909–912.
[8] a) J. Drew, M. Letellier, P. Morand, A. G. Szabo, J. Org. Chem.
1987, 52, 4047–4052; b) S. Misumi, M. Nakagawa, Bull. Chem.
Soc. Jpn. 1963, 36, 399–404; c) Y. Ishii, C. Gao, W.-X. Xu, M.
Iwasaki, M. Hidai, J. Org. Chem. 1993, 58, 6818–6825; d)
A. M. Reddy, V. J. Rao, J. Org. Chem. 1992, 57, 6727–6731.
[9] a) A. A. Baum, Tetrahedron Lett. 1972, 13, 1817–1820; b)
W. A. Bowman, P. T. Stephenson, A. R. Young, Tetrahedron
1995, 51, 11445–11456; c) M. Tokuda, H. Fujita, T. Miyamato,
H. Suginome, Tetrahedron 1993, 49, 2413–2426.
[10] Occasionally, penta-2,4-dien-1-ol 2a can be obtained in low
yield as a byproduct in the isomerization of substrate 1g.
[11] For some selected papers, see: a) S.-L. Huang, K. Omura, D.
Swern, J. Org. Chem. 1976, 41, 3329–3331; b) S.-L. Huang, K.
Omura, D. Swern, Synthesis 1978, 297–298; c) A. J. Mancuso,
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[12] Crystal data of 6h: Empirical Formula: C14H16O4; Formula
weight: 248.27; crystal color, habit: colorless, prismatic; crystal
dimensions: 0.517ϫ0.505ϫ0.397 mm; crystal system: mono-
General Procedure for the Pd-Catalyzed Isomerization of Methyl-
enecyclopropanecarbaldehydes (E)-5: Under an argon atmosphere,
a mixture of 5e (0.5 mmol), Pd(PPh3)4 (0.05 mmol), and AsPh3
(0.1 mmol) in toluene (2.0 mL) was heated to 100 °C. Then, AcOH
(0.5 mmol) was added into the solution dropwise. The reaction
mixture was stirred at 100 °C for 2.5 h. Then, the solvent was re-
moved under reduced pressure, and the residue was purified on a
silica gel column chromatography to give product 6a as a yellow
liquid.
General Procedure for the Pd-Catalyzed Reactions of Methylene-
cyclopropanecarbaldehydes (Z)-5: Under an argon atmosphere, a
mixture of 5a (0.5 mmol), Pd(PPh3)4 (0.05 mmol), and AsPh3
(0.1 mmol) in toluene (2.0 mL) was heated to 100 °C. Then, AcOH
(0.5 mmol) was added into the solution dropwise. The reaction
mixture was stirred at 100 °C for 2.5 h. Then, the solvent was re-
moved under reduced pressure, and the residue was purified by a
silica gel column chromatography to give product 7a as an orange
liquid.
Supporting Information (see footnote on the first page of this arti-
cle): General methods and procedures, results using HCOOH as
the acid source, and spectroscopic data.
Acknowledgments
clinic; lattice type: primitive; lattice parameters:
a =
Financial support from the Shanghai Municipal Committee of Sci-
ence and Technology (06XD14005 and 08dj1400100-2), National
Basic Research Program of China [(973)-2009CB825300], and the
10.869(2) Å, b = 14.124(3) Å, c = 17.504(3) Å, α = 90°, β =
103.901(3)°, γ = 90°, V = 2608.5(9) Å3; space group: P21/c; Z =
8; Dcalcd. = 1.264 g/cm3; F(000) = 1056; diffractometer: Rigaku
6452
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Eur. J. Org. Chem. 2010, 6448–6453