Categories: C-C Bond Formation > Cyclic compounds > Cycloalkanes

Synthesis of cyclopropanes

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Name Reactions

Wurtz Reaction (intramolecular modification)

Recent Literature

Suitable conditions enable the Suzuki-Miyaura coupling reaction of potassium cyclopropyl- and cyclobutyltrifluoroborates in moderate to excellent yield with electron-rich, electron-poor, and hindered aryl chlorides to give various substituted aryl cyclopropanes and cyclobutanes.
G. A. Molander, P. E. Gormisky, J. Org. Chem., 2008, 73, 7481-7485.

The palladium-catalyzed cross-coupling reaction of tricyclopropylbismuth with aryl and heterocyclic halides and triflates tolerates numerous functional groups and does not require anhydrous conditions. The method was successfully extended to the cross-coupling of triethylbismuth.
A. Gagnon, M. Duplessis, P. Alsabeh, F. Barabé, J. Org. Chem., 2008, 73, 3452-3459.

A class of zinc reagents (RXZnCH₂Y) is very effective for the cyclopropanation of olefins. The reactivity and selectivity of these reagents can be regulated by tuning the electronic and steric nature of the RX group. A reasonable level of enantioselectivity was obtained for the cyclopropanation of unfunctionalized olefins with chiral (iodomethyl)zinc species.
J. C. Lorenz, J. Long, Z. Yang, S. Xue, X. Xie, Y. Shi, J. Org. Chem., 2004, 69, 209-212.

A mixture of ZnI₂, EtZnI·2OEt₂ and CHI₃ produces a gem-dizinc carbenoid that is an efficient cyclopropanating reagent, which shortens reaction times and leads to cleaner reactions, particularly with less reactive substrates. Mechanistic aspects of the reaction are discussed.
J.-F. Fournier, A. B. Charette, Eur. J. Org. Chem., 2004, 1401-1404.

A new class of anionic, boron-bridged analogues of the box ligands was developed. These borabox ligands showed a considerable potential for asymmetric cyclopropanation and desymmetrizations of meso diols.
C. Mazet, V. Koehler, A. Pfaltz, Angew. Chem. Int. Ed., 2005, 44, 4888-4891.

In a Rh-catalyzed procedure for the cyclopropanation of alkenes with α-alkyl-α-diazoesters, sterically demanding carboxylate ligands serve to avoid β-hydride elimination. The use of triphenylacetate (TPA) as ligand also imparts high diastereoselectivity.
P. Panne, A. DeAngelis, J. M. Fox, Org. Lett., 2008, 10, 2987-2989.

A samarium-promoted cyclopropanation can be carried out on unmasked (E)- or (Z)-α,β-unsaturated carboxylic acids. In all cases the process is completely stereospecific and stereoselective. A mechanism has been proposed.
J. M. Concellón, H. Rodríguez-Solla, C. Simal, Org. Lett., 2007, 9, 2685-2688.

Efficient, simple, cheap, and environmentally benign preparations of cyclopropanes were achieved. One method is based on a 3-exo-trig cyclisation of various electron-deficient 2-iodoethyl-substituted olefins with zinc powder in a mixture of t-butyl alcohol and water, and the other on a 3-exo-tet cyclisation of various 1,3-dihalopropanes with zinc powder in ethanol.
D. Sakuma, H. Togo, Tetrahedron, 2005, 61, 10138-10145.

D. Sakuma, H. Togo, Tetrahedron, 2005, 61, 10138-10145.

Methyl 1-aryl-2-amino-cyclopropane carboxylates have been readily synthesized in high yields by Rh-catalyzed decomposition of aryldiazoacetates in the presence of N-vinylphthalimide. The reaction is highly trans-selective.
T. Melby, R. A. Hughes, T. Hansen, Synlett, 2007, 2277-2279.

The first Corey-Chaykovsky epoxidation and cyclopropanation using trimethyl sulfonium iodide/trimethyl sulfoxonium iodide and KOH as base in the recyclable ionic liquid, (bmim)PF₆ are described.
S. Chandrasekhar, Ch. Narasihmulu, V. Jagadeshwar, K. Venkatram Reddy, Tetrahedron Lett., 2003, 44, 3629-3630.

(S)-(-)-indoline-2-yl-1H-tetrazole readily facilitates the enantioselective organocatalytic cyclopropanation of α,β-unsaturated aldehydes with sulfur ylides, providing cyclized product in excellent diastereoselectivities and enantioselectivities.
A. Hartikka, P. I. Arvidsson, J. Org. Chem., 2007, 72, 5874-5877.

Three highly enantio- and diastereoselective one-pot procedures for the synthesis of cyclopropyl and iodocyclopropyl alcohols with up to four contiguous stereocenters are reported. Route 1 and 2 involve asymmetric addition of an alkylzinc reagent to an enal followed by diastereoselective cyclopropanation using either diiodomethane or iodoform to generate the zinc carbenoid, leading to cyclopropyl or iodocyclopropyl alcohols, respectively. Route 3 entails asymmetric vinylation of an aldehyde with divinylzinc reagents and subsequent diastereoselective cyclopropanation.
H. Y. Kim, A. E. Lurain, P. Garcia-Carcia, P. J. Carroll, P. J. Walsh, J. Am. Chem. Soc., 2005, 127, 13138-13139.

H. Y. Kim, A. E. Lurain, P. Garcia-Carcia, P. J. Carroll, P. J. Walsh, J. Am. Chem. Soc., 2005, 127, 13138-13139.

An organocatalytic asymmetric cascade Michael reaction of α,β-unsaturated aldehydes with bromomalonates, efficiently catalyzed by chiral diphenylprolinol TMS ether in the presence of base 2,6-lutidine, gives cyclopropanes in high enantio- and diastereoselectivities. Using NaOAc as base, a spontaneous ring-opening of cyclopropanes leads to (E) α-substituted malonate α,β-unsaturated aldehydes.
H. Xie, L. Zu, H. Li, J. Wang, W. Wang, J. Am. Chem. Soc., 2007, 129, 10886-10894.

The reaction of 1-aryl-2,2,2-trifluorodiazoethanes with alkenes provides trifluoromethyl-substituted cyclopropanes with high diastereoselectivity and enantioselectivity in the presence of an adamantylglycine-derived dirhodium complex Rh₂(R-PTAD)₄ as catalyst.
J. R. Denton, D. Sukumaran, H. M. L. Davies, Org. Lett., 2007, 9, 2625-2628.

An efficient lithium amide-induced intramolecular cyclopropanation of bishomoallylic and trishomoallylic epoxides is described. The methodology is used in an asymmetric synthesis of sabina ketone.
D. M. Hodgson, Y. K. Chung, J.-M. Paris, J. Am. Chem. Soc., 2004, 126, 8654-8655.

Exposure of enynes containing a hydroxyl group at one of the propargylic positions to catalytic amounts of either PtCl₂ or (PPh₃)AuCl/AgSbF₆ results in a selective rearrangement with formation of bicyclo[3.1.0]hexan-3-one derivatives. A total synthesis of the terpenes sabinone and sabinol is described.
V. Mamane, T. Gress, H. Krause, A. Fürstner, J. Am. Chem. Soc., 2004, 126, 8654-8655.

V. Mamane, T. Gress, H. Krause, A. Fürstner, J. Am. Chem. Soc., 2004, 126, 8654-8655.

The reaction of various 1,6-enynes with N₂CHSiMe₃ in the presence of RuCl(COD)Cp* as catalyst precursor leads to the general formation of alkenylbicyclo[3.1.0]hexanes at room temperature in good yield with high stereoselectivity. The catalytic formation of alkenylbicyclo[3.1.0]hexanes also takes place in the presence of N₂CHCO₂Et or N₂CHPh.
F. Monnier, C. Vovard-Le Bray, D. Castillo, V. Aubert, S. Dérien, P. H. Dixneuf, L. Toupet, A. Ienco, C. Mealli, J. Am. Chem. Soc., 2007, 129, 6037-6049.

F. Monnier, C. Vovard-Le Bray, D. Castillo, V. Aubert, S. Dérien, P. H. Dixneuf, L. Toupet, A. Ienco, C. Mealli, J. Am. Chem. Soc., 2007, 129, 6037-6049.

A new Pd-catalyzed oxidation reaction for the stereospecific conversion of enynes into cyclopropyl ketones proceeds with net inversion of geometry with respect to the starting olefin. This result is consistent with a mechanism in which the key cyclopropane-forming step involves nucleophilic attack of a tethered olefin onto the Pd^IV-C bond.
L. L. Welbes, T. W. Lyons, K. A. Cychosz, M. S. Sanford, J. Am. Chem. Soc., 2007, 129, 5836-5837.