Direct Cyclopropanation of 1-Alkynylphosphonates
were formed instead. While Cp2ZrCl2/2EtMgBr is a known
reagent,22 Cp2ZrCl2/2EtMgBr/2AlCl3 has been recently re-
ported.23
Results and Discussion
The zirconacyclopentenylphosphonate 2b was obtained in
>97% (based on GCMS and NMR analysis) from Cp2ZrCl2/
2EtMgBr. Intermediates 2 are thermally stable at room tem-
perature and smoothly insert various electrophiles.24 Surpris-
ingly, during our present effort to insert other functional groups
to 2b, we found that addition of 2 equiv of AlMe3 or AlEt3 led
to the exclusive formation of cyclopropylmethyl phosphate 3b
in 65% yield (based on 31P NMR). Optimization of the reaction
conditions by using AlCl3 rather than AlR3 improved the yield
of 3b to 95% (eq 1).
(10) Cyclopropanation of unsaturated phosphonates by copper-catalyzed
decomposition of ethyl diazoacetate: (a) Seyferth, D.; Marmor, R.; Hilbert,
P. J. Org. Chem. 1971, 36, 1379-1386. (b) Tsuji, T.; Nishida, S. In The
Chemistry of the Cyclopropyl Group; Rappoport, Z., Ed.; John Wiley and
Sons Ltd.: Chi-Chester, 1987; Chapter 7, pp 330-333. (c) Paul-Roth, C.;
De Montigny, F.; Rethore, G.; Simonneaux, G.; Gulea, M.; Masson, S. J.
Mol. Catal. A: Chem. 2003, 201, 79-91. (d) Simonneaux, G.; De Montigny,
F.; Paul-Roth, C.; Gulea, M.; Masson, S. Tetrahedron Lett. 2002, 43, 3685-
3687. (e) Lewis, R. T.; Motherwell, W. B. Tetrahedron Lett. 1988, 29,
5033-5036. (f) Lewis, R. T.; Motherwell, W. B.; Shipman, M.; Slawin,
A. M. Z.; Williams, D. J. Tetrahedron 1995, 51, 3289-3302. Arbuzov
reaction of 1-methyl-2,2-dichlorocyclopropylcarbonyl chlorides with
P(OR)3: Mitrasov, Yu. N.; Simakova, E. A.; Antonova, I. I.; Krasnova, A.
A.; Alekseeva, O. O.; Skvortsov, V. G. Russ. J. Gen. Chem. 2004, 74, 637-
638 (CAN 141:243627 AN 2004:485032). Rearrangement of epoxyphos-
phonates: Kuznetsova, N. G.; Amori, L.; Pelicciari, R. Ufim. Russ.
Bashkirskii Khim. Zh. 2002, 9, 40-41 (CAN 139:149676 AN 2003:120994).
Amination/phosphonation of alkylcyclopropanone acetals to give the
corresponding aminophosphonates: Tesson, N.; Dorigneux, B.; Fadel.
Tetrahedron: Asymmetry 2002, 13, 2267-2276. Reaction of cobalt(0) or
magnesium on R-(halomethyl)phosphonates and c-PrCOOR to give
c-PrCOCH2P(O)(OEt)2: Orsini, F.; Di Teodoro, E.; Ferrari, M. Synthesis
2002, 1683-1688. Michael induced ring closure (MIRC) of trialkyl
phosphites with the corresponding R-bromoalkylidene cyanoacetates and
malonates: Stevens, C. V.; Van Heecke, G.; Barbero, C.; Patora, K.; De
Kimpe, N.; Verhe, R. Synlett 2002, 1089-1092. 1,3-Dipolar cycloaddition
of diazomethane to 1,1-difluoroallylphosphonates followed by photolysis:
Yokomatsu, T.; Suemune, K.; Murano, T.; Shibuya, S. Heterocycles 2002,
56, 273-282. 1,3-Dipolar addition of diazomethane to 1-acetoxyphospho-
nates followed by thermolysis: Chen, R.; Liu, Z.; Chen, L. Gaodeng Xuexiao
Huaxue Xuebao 1988, 9, 295-2977 (CAN 110:75647 AN 1989:75647).
Reaction of phosphorane or arsorane with diisopropyl (E)-(3,3,3-trifluoro-
prop-1-en-1-yl)phosphonate to give trifluoromethylated cyclopropylphos-
phonates: Shen, Y.; Qi, M. J. Chem. Res. Synop. 1996, 328-329. Reaction
of cyclopropanes with Et2PCl followed by H2S and Arbuzov reaction with
(PrO)3: Kormachev, V. V.; Bolesov, I. G.; Ishmuratov, A. S. Zh. Obshch.
Khim. 1987, 57, 704-7055 (CAN 108:21972 AN 1988:21972). Lithiation
of ClCH2P(O)(OEt)2 and reaction with RR1CO to give epoxyalkylphos-
phonates: Coutrot, P.; Savignac, P. Synthesis 1978, 34-36. Intramolecular
cyclization of 2-allylbenzoylphosphonates with trimethyl phosphite via
carbine intermediates: Griffiths, D. V.; Harris, J. E.; Karim, K.; Whitehead,
gj17.htm. Double olefination of 1,1-bis phosphonates to give 4-alkyl-1,3-
butadienylphosphonates: Shen, Y.; Li, P.; Ni, J.; Sun, J. J. Org. Chem. 1998,
63, 9396-9398. Peterson olefination of the reaction of aldehydes and
ketones to R-lithiated-R-fluoro-R-trimethylsilymethylphosphonate: Wasch-
busch, R.; Carran, J.; Savignac, P. Tetrahedron 1996, 52, 14199-14216.
Reaction of RR1C:CH2 with (MeO)2P(O)H to give RR1CHCH2P(O)(OMe)2:
Kormachev, V. V.; Mitrasov, Y. N.; Anisimova, E. A.; Kolyamshin, O. A.
Zh. Obshch. Khim. 1992, 62, 1428-29 (CAN 118:102083 AN 1993:
102083). Bis-alkylation of R-functional methylphosphonates with dibro-
moalkanes in the presence of base: Nasser, J.; About-Jaudet, E.; Collignon,
N. Phosphorus, Sulfur Silicon Relat. Elem. 1990, 54, 171-179. Addition
of organolithium reagents to di-Et 1-(trimethylsilyl)vinylphosphonate fol-
lowed by quenching with acid chlorides and alkyl isocyanates: Hong, S.;
Chang, K.; Ku, B.; Oh, D. Y. Tetrahedron Lett. 1989, 30, 3307-3308.
Various transformations of existing cyclopropylphosphonates: (g) from
1-hydroxyiminophosphonates and their reduction with NaBH4 in the
presence of transition metal compounds to give 1-aminophosphonates:
Demir, A. S.; Tanyeli, C.; Sesenoglu, O.; Demic, S.; Evin, O. O. Tetrahedron
Lett. 1996, 37, 407-10. (h) by formylation of 1,1-dialkylphoasphonates:
Teulade, M. P.; Savignac, P. Synth. Commun. 1987, 17, 125-136. (i) by
reductive amination of â-ketophosphonates: Varlet, J. M.; Collingnon, N.;
Savignac, P. Tetrahedron 1981, 37, 3713-3721. (j) (E)-Vinylphosphonates
by indium-promoted borohydride reduction of alkynylphosphonates: Wang,
C.; Pan, Y.; Yang, D. China J. Organomet. Chem. 2005, 690, 1705-1709
(CAN 142:482099 AN 2005:280585). (k) Phosphaisocoumarins by Cu(I)-
catalyzed intramolecular cyclization of o-ethynylphenylphosphonic acid
monoethyl esters: Peng, A.-Y.; Ding, Y.-X. J. Am. Chem. Soc. 2003, 125,
15006-15007. (l) Cyclopropane nucleotide analogues by reduction of
cyclopropylalkanones possessing a difluoromethylenephosphonate group at
the ring: Yokomatsu, T.; Yamagishi, T.; Suemune, K.; Abe, H.; Kihara,
T.; Soeda, S.; Shimeno, H.; Shibuya, S. Tetrahedron 2000, 56, 7099-7108.
(m) Addition of cyclopropylphosphonates to aldehydes: Hirao, T.; Naka-
mura, T.; Hagihara, M.; Agawa, T. J. Org. Chem. 1985, 50, 5860-5862.
The temperature is crucial for the course of the reaction. We
found that AlCl3 must be added to 2b at -30 to -40 °C, after
which the reaction is maintained at the same temperature for 1
h and is quenched with dilute HCl. Adding AlCl3 at a higher
temperature or allowing the temperature to rise above -30 °C
resulted in the formation of predominantly ethylated vinylphos-
phonates (eq 2). Also, 2 equiv of AlCl3 is essential for optimum
yield; using less than 2 equiv of AlCl3 substantially decreased
the yield of 3b. The products 3 were extracted, separated on
(11) For a review of cyclopropylmethylmetal reagents, see: Houben-
Weyl, Methods of Organic Chemistry; de Meijere, A., Ed.; Thieme:
Stuttgart, 1997; Vol. E17, p 2686 and references therein.
(12) (a) Dzhemilev, U. M.; Ibragimov, A. G.; Khafizova, L. O.;
Ramazanov, I. R.; Yalalova, D. F.; Tolstikov, G. A. J. Organomet. Chem.
2001, 636, 76-81. (b) A Review: Dzhemilev, U. M.; Ibragimov, A. G.
Russ. Chem. Bull. 1998, 47, 786-794.
(13) Gandon, V.; Laroche, C.; Szymoniak, J. Tetrahedron Lett. 2003,
44, 4827-4829.
(14) (a) Ito, H.; Kuroi, H.; Ding, H.; Taguchi, T. J. Am. Chem. Soc.
1998, 120, 6623-6624. (b) Ito, H.; Sato, A.; Kusanagi, T.; Taguchi, T.
Tetrahedron Lett. 1999, 40, 3397-3398.
(15) Negishi, E.; Montehamp, J. L.; Anastasia, L.; Elizarov, A.; Choueiry,
D.-le. Tetrahedron Lett. 1998, 39, 2503-2506.
(16) Montchamp, J.-L.; Negishi, E. J. Am. Chem. Soc. 1998, 120, 5345-
5346.
(17) Kulinkovich, O. G.; de Meijere, A. Chem. ReV. 2000, 100, 2789-
2834.
(18) (a) Fujita, K.; Yorimitsu, H.; Shinokubo, H.; Oshima, K. J. Am.
Chem. Soc. 2004, 126, 6776-6783. (b) Gandon, V.; Bertus, P.; Szymoniak,
J. Eur. J. Org. Chem. 2000, 3713-3719.
(19) Dembitsky, V. M.; Aziz Quntar, A. A.; Haj-Yehia, A.; Srebnik, M.
Mini ReV. Org. Chem. 2005, 2, 343-357.
(20) Aziz Quntar, A. A.; Srebnik, M. J. Organomet. Chem. 2005, 690,
2504-2514.
(21) Aziz Quntar, A. A.; Srebnik, M. Chem. Commun. 2003, 58-59.
(22) (a) Negishi, E.; Takahashi, T. Bull. Chem. Soc. Jpn. 1998, 71, 755.
(b) Negishi, E.; Takahashi, T. Acc. Chem. Res. 1994, 27, 124-130.
(23) Xi, Li, Z. Top. Organomet. Chem. 2004, 10, 27-56.
(24) Ben-Valid, S.; Aziz Quntar, A. A.; Srebnik, M. J. Org. Chem. 2005,
70, 3554-3559.
J. Org. Chem, Vol. 71, No. 2, 2006 731