Organic Letters
Letter
Pannecoucke, X. Syntheses and Applications of Monofluorinated
Cyclopropanes. Chem. - Eur. J. 2012, 18, 14904−14917. Example of
other halocyclopropanes: (c) Charette, A. B.; Gagnon, A.; Fournier, J.-
F. First Evidence for the Formation of a Geminal Dizinc Carbenoid: A
Highly Stereoselective Synthesis of 1,2,3-Substituted Cyclopropanes. J.
Am. Chem. Soc. 2002, 124, 386−387.
(5) For fluorodiazomethane, see: (a) Boldyrev, A. I.; Schleyer, P. V. R.;
Higgins, D.; Thomson, C.; Kramarenko, S. S. Ab Initio Investigation of
the Structures and Stabilities of CH2N2, CHFN2, and CF2N2 Isomers:
Important Consequences of MP2 Optimizations. J. Comput. Chem.
Dichlorocyclopropanes to Olefins. J. Chem. Soc. C 1969, 165172.
(b) Cottens, S.; Schlosser, M. Attempted and Accomplished Syntheses
of a Few Monofluorinated Chrysanthemic Acid Derivatives. Tetrahe-
dron 1988, 44, 7127−7144. (c) Pons, A.; Beucher, H.; Ivashkin, P.;
Lemonnier, G.; Poisson, T.; Charette, A. B.; Jubault, P.; Pannecoucke,
X. Rhodium-Catalyzed Cyclopropanation of Fluorinated Olefins: A
Straightforward Route to Highly Functionalized Fluorocyclopropanes.
Org. Lett. 2015, 17, 1790−1793. (d) Hirotaki, K.; Takehiro, Y.;
Kamaishi, R.; Yamada, Y.; Hanamoto, T. Synthesis of Mono-
Fluorinated Functionalized Cyclopropanes and Aziridines Using the
α-Fluorovinyl Diphenyl Sulfonium Salt. Chem. Commun. 2013, 49,
7965−7967.
́
1992, 13, 1066−1078. (b) Zapata, L. A.; Lopez, S.; Ruiz, P.; Quijano, J.;
Notario, R. Halodiazirines and Halodiazo Compounds: a Computa-
tional Study of Their Thermochemistry and Isomerization Reaction.
Struct. Chem. 2017, 28, 597−605. For other fluorinated diazoalkanes,
see: (c) Mertens, L.; Koenigs, R. M. Fluorinated Diazoalkanes − a
Versatile Class of Reagents for the Synthesis of Fluorinated
Compounds. Org. Biomol. Chem. 2016, 14, 10547−10556.
(10) For selected examples of the direct fluorination of cyclopropanes,
see: (a) Kirihara, M.; Kakuda, H.; Tsunooka, M.; Shimajiri, A.; Takuwa,
T.; Hatano, A. Reaction of Tertiary Cyclopropyl Silyl Ethers with
Diethylaminosulfur Trifluoride: the Effects of Substituents on the
Cleavage of the Cyclopropane Ring. Tetrahedron Lett. 2003, 44, 8513−
8518. (b) Yang, Y.; Su, C.; Huang, X.; Liu, Q. Halohydroxylation of
Alkylidenecyclopropanes Using N-Halosuccinimide (NXS) as the
Halogen Source: an Efficient Synthesis of Halocyclopropylmethanol
and 3-Halobut-3-En-1-Ol Derivatives. Tetrahedron Lett. 2009, 50,
5754−5756. (c) Zhang, M.; Gong, Y.; Wang, W. A Two-Step Sequence
to Ethyl α-Fluorocyclopropanecarboxylates Through MIRC Reaction
of Ethyl Dichloroacetate and Highly Regioselective Fluorination. Eur. J.
Org. Chem. 2013, 2013, 7372−7381.
(6) For a review on fluorinated carbenes: (a) Brahms, D. L. S.; Dailey,
W. P. Fluorinated Carbenes. Chem. Rev. 1996, 96, 1585−1632. For
CHFBr2 as a reagent for monofluorocarbene generation: (b) Schlosser,
M.; Heinz, G. Monofluorocarbene and its syn/anti Selectivity. Angew.
Chem., Int. Ed. Engl. 1968, 7, 820−821; Angew. Chem. 1968, 80, 849−
850. For CHFI2 as a reagent for monofluorocarbene generation, see:
(c) Hahnfeld, J. L.; Burton, D. J. Monofluorocarbene: The Synthesis of
Fluorocyclopropanes. Tetrahedron Lett. 1975, 16, 1819−1822.
(d) Tamura, O.; Hashimoto, M.; Kobayashi, Y.; Katoh, T.; Nakatani,
K.; Kamada, M.; Hayakawa, I.; Akiba, T.; Terashima, S. Synthesis and
Optical Resolution of dl-cis-2-Fluorocycloproplylamine, the Key
Component of the New Generation of Quinolonecarboxylic Acid,
DU-6859. Tetrahedron Lett. 1992, 33, 3483−3486. (e) Nishimura, J.;
Furukawa, J. The Formation of a Halogenocarbenoid of Zinc. A Novel
Synthetic Route to Halogenocyclopropane Derivatives. J. Chem. Soc. D
1971, 1375−1376. (f) Kawabata, N.; Tanimoto, M.; Fujiwara, S.
Synthesis of Monohalocyclopropane Derivatives from Olefins by the
Reaction with Trihalomethanes and Copper. Tetrahedron 1979, 35,
1919−1923. For CHF2I as a reagent for monofluorocarbene
generation, see: (g) Beaulieu, L.-P. B.; Schneider, J. F.; Charette, A.
B. Highly Enantioselective Simmons−Smith Fluorocyclopropanation
of Allylic Alcohols via the Halogen Scrambling Strategy of Zinc
Carbenoids. J. Am. Chem. Soc. 2013, 135, 7819−7822. (h) Navuluri, C.;
Charette, A. B. Diastereoselective Fluorocyclopropanation of Chiral
Allylic Alcohols Using an α-Fluoroiodomethylzinc Carbenoid. Org.
Lett. 2015, 17, 4288−4291.
(7) Indirect methods for the introduction of monofluoromethylene
synthon. For example, via halofluorocarbene: (a) Oliver, J.; Rao, U.;
Emerson, M. Synthesis of Monofluorocyclopropane Derivatives.
Tetrahedron Lett. 1964, 5, 3419−3425. (b) Ando, T.; Yamanaka, H.;
Namigata, F.; Funasaka, W. Reduction of Gem-Halofluorocyclopro-
panes with Tributyltin Hydride. J. Org. Chem. 1970, 35, 33−38. Via
chlorofluoromethyl phenyl sulfide: (c) Kirihara, M.; Ogata, T.; Itou, A.;
Naito, S.; Kishida, M.; Yamazaki, K.; Tabata, H.; Takahashi, H.
Synthesis of Monofluoromethylcyclopropanes from Alkenes without
Using Freons: Novel Synthesis of Chlorofluoromethyl Phenyl Sulfide
and Its Application in Cyclopropanation. Chem. Lett. 2013, 42, 1377−
1379. (d) Ivashkin, P.; Couve-Bonnaire, S.; Jubault, P.; Pannecoucke,
X. One-Step Synthesis of Highly Functionalized Monofluorinated
Cyclopropanes from Electron-Deficient Alkenes. Org. Lett. 2012, 14,
2270−2273. (e) Ivashkin, P.; Couve-Bonnaire, S.; Jubault, P.;
Pannecoucke, X. Asymmetric Synthesis of Cyclopropanes with a
Monofluorinated Quaternary Stereocenter. Org. Lett. 2012, 14, 5130−
5133.
(11) See ref 4.
(12) On fluorocarbenoids, see: (a) Kail, D. C.; Malova Krizkova, P.;
Wieczorek, A.; Hammerschmidt, F. On the Configurational Stability of
Chiral, Nonracemic Fluoro- and Iodo-[D1]Methyllithiums. Chem. -
Eur. J. 2014, 20, 4086−4091. (b) Molitor, S.; Gessner, V. H. Alkali
Metal Chlorine and Bromine Carbenoids: Their Thermal Stability and
Structural Properties. Chem. - Eur. J. 2017, 23, 12372−12379. (c) Parisi,
G.; Colella, M.; Monticelli, S.; Romanazzi, G.; Holzer, W.; Langer, T.;
Degennaro, L.; Pace, V.; Luisi, R. Exploiting a “Beast” in Carbenoid
Chemistry: Development of a Straightforward Direct Nucleophilic
Fluoromethylation Strategy. J. Am. Chem. Soc. 2017, 139, 13648−
13651. (d) Monticelli, S.; Colella, M.; Pillari, V.; Tota, A.; Langer, T.;
Holzer, W.; Degennaro, L.; Luisi, R.; Pace, V. Modular and
Chemoselective Strategy for the Direct Access to α-Fluoroepoxides
and Aziridines via the Addition of Fluoroiodomethyllithium to
Carbonyl-Like Compounds. Org. Lett. 2019, 21, 584−588. (e) Colella,
M.; Tota, A.; Großjohann, A.; Carlucci, C.; Aramini, A.; Sheikh, N. S.;
Degennaro, L.; Luisi, R. Straightforward Chemo- and Stereoselective
Fluorocyclopropanation of Allylic Alcohols: Exploiting the Electro-
philic Nature of the Not so Elusive Fluoroiodomethyllithium. Chem.
Commun. 2019, 55, 8430−8433.
(13) Veliks, J.; Kazia, A. Fluoromethylene Transfer from Diary-
lfluoromethylsulfonium Salts: Synthesis of Fluorinated Epoxides. Chem.
- Eur. J. 2019, 25, 3786−3789.
(14) (a) Prakash, G. K. S.; Ledneczki, I.; Chacko, S.; Olah, G. A. Direct
Electrophilic Monofluoromethylation. Org. Lett. 2008, 10, 557−560.
(b) SciFinder search in 06.2019 lists six vendors for sulfonium salt 1.
̈
(15) Allgauer, D. S.; Jangra, H.; Asahara, H.; Li, Z.; Chen, Q.; Zipse,
H.; Ofial, A. R.; Mayr, H. Quantification and Theoretical Analysis of the
Electrophilicities of Michael Acceptors. J. Am. Chem. Soc. 2017, 139,
13318−13329.
(16) Melendo, A. B. B.; Agejas-Chicharro, F. J. WO patent
2010080333A1.
(17) (a) Patel, S.; Hamilton, G.; Stivala, C.; Chen, H.; Daniels, B. U.S.
Pat. (2019), US 20190127382 A1. (b) Fan, L.; Xu, K.; Chen, K.;
Zhang, S.; Du, W.; Li, X.; Chen, Y. PCT Int. Appl. (2018), WO
2018210207 A1.
(18) Carta, F.; Scozzafava, A.; Supuran, C. T. Sulfonamides: a Patent
Review (2008 − 2012). Expert Opin. Ther. Pat. 2012, 22, 747−758.
(19) Zimmerman, H. E.; Thyagarajan, B. S. The Stereochemistry of
Sulfone-Stabilized Carbanions. J. Am. Chem. Soc. 1960, 82, 2505−2511.
(20) Aggarwal, V. K.; Richardson, J. The Complexity of Catalysis:
Origins of Enantio- and Diastereocontrol in Sulfur Ylide Mediated
Epoxidation Reactions. Chem. Commun. 2003, 2644.
(8) Shen, X.; Zhang, W.; Zhang, L.; Luo, T.; Wan, X.; Gu, Y.; Hu, J.
Enantioselective Synthesis of Cyclopropanes That Contain Fluorinated
Tertiary Stereogenic Carbon Centers: A Chiral α-Fluoro Carbanion
Strategy. Angew. Chem., Int. Ed. 2012, 51, 6966−6970; Angew. Chem.
2012, 124, 7072−7076.
(9) For selected examples of fluorocyclopropane synthesis from
fluorinated alkenes, see: (a) Fields, R.; Haszeldine, R. N.; Peter, D.
Cyclopropane Chemistry. Part I. Thermal Isomerisation of Gem-
E
Org. Lett. XXXX, XXX, XXX−XXX