Page 5 of 6
Journal of the American Chemical Society
Polyvalent Iodine Compounds; John Wiley & Sons Ltd.: New York,
113, PR179−PR233. (b) Reed, C. A. H+, CH3+, and R3Si+ Carborane
Reagents: When Triflates Fail. Acc. Chem. Res. 2010, 43, 121–128.
(c) Reed, C. A. Carboranes:ꢀ A New Class of Weakly Coordinating
Anions for Strong Electrophiles, Oxidants, and Superacids. Acc.
Chem. Res. 1998, 31, 133–139.
2014. and references therein.
1
2
3
4
5
6
7
8
2. (a) Aradi, K.; Tóth, B. L.; Tolnai, G. L.; Novák, Z. Diaryliodonium
Salts in Organic Syntheses: A Useful Compound Class for Novel
Arylation Strategies. Synlett 2016, 27, 1456–1485. (b) Merritt, E. A.;
Olofsson, B. Diaryliodonium Salts: A Journey from Obscurity to
Fame. Angew. Chem., Int. Ed. 2009, 48, 9052–9070. (c) Hypervalent
Iodine Chemistry. Topics in Current Chemistry; Wirth, T. Ed.;
Springer: Cham, 2016; Vol. 373.
3. (a) Yaws, C. L.; Braker, W. Matheson Gas Data Book, McGraw-Hill,
New York, 2001. (b) Gutmann, V. Die Chemie in Bromtrifluorid.
Angew. Chem. 1950, 62, 312–315.
13. p-TfOC6H4Cl afforded only 17% of desired product even after 48 h.
14. Structural data can be retrieved from CSD (CCDC 1887417).
15. For similar onium-type structures of Me2Cl+ and Et2Cl+ salts, see:
Stoyanov, E. S.; Stoyanova, I. V.; Tham, F. S.; Reed, C. A. Dialkyl
Chloronium Ions. J. Am. Chem. Soc. 2010, 132, 4062–4063.
16. Phenylation of 2-(methoxycarbonyl)-1-indanone with various
diaryl-λ3-iodanes required a longer reaction time. (a) Ochiai, M.;
Kitagawa, Y.; Takayama, N.; Takaoka, Y.; Shiro, M. Synthesis of
Chiral Diaryliodonium Salts, 1,1’-Binaphthyl-2-yl(phenyl)iodonium
Tetrafluoroborates:ꢀ Asymmetric α-Phenylation of β-Keto Ester
Enolates. J. Am. Chem. Soc. 1999, 121, 9233–9234. (b) Ochiai, M.;
Kitagawa, Y.; Toyonari, M. On the mechanism of α-phenylation of
β-keto esters with diaryl-λ3-iodanes: evidence for a non-radical
pathway. ARKIVOC 2003, 6, 43–48.
4. (a) Nesmeyanov, A. N.; Tolstaya, T. P.; Isaeva, L. S.
Diphenylbromonium Salts. Dokl. Akad. Nauk SSSR 1955, 104, 872–
875. For Improved Synthesis of Diaryl-λ3-bromanes, see: (b)
Vanchikov, A. N.; Lisichkina, I. N.; Grushin, V. V.; Tolstaya, T. P.
Арипрование трифторида ьрома тетраарилстаннанами. Dokl. Akad.
Nauk SSSR 1980, 255, 1386–1389. (c) Frohn, H.-J.; Giesen, M.;
Welting, D.; Bardin, V. V. Bis(perfluoroorganyl)bromonium Salts
[(RF)2Br]Y (RF = Aryl, Alkenyl, and Alkynyl). J. Fluorine Chem.
2010, 131, 922–932. Reviews: (d) Farooq, U.; Shah, A. A.; Wirth, T.
Hypervalent Bromine Compounds: Smaller, More Reactive
Analogues of Hypervalent Iodine Compounds. Angew. Chem., Int.
Ed. 2009, 48, 1018–1020. (e) Ochiai, M. Hypervalent Aryl-, Alkynyl-,
and Alkenyl-λ3-bromanes. Synlett 2009, 159–173.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
17. The selectivity of arylation of 3aa-BArf4 was comparable to that
reported for aryl(mesityl)-λ3-iodanes. The reactivity trend is
dependent on the balance of nucleophilicity/steric hindrance of
nucleophiles. For details of the arylation selectivity of
diaryl-λ3-iodanes, see references 1 and 2.
18. The reaction of diphenyl(tetrafluoroborato)-λ3-chlorane with
pyridine has been investigated, and the N-phenylpyridinium salt was
obtained in high yield (115 ºC, 14.5 h, 88%). See reference 5. For the
reaction of bromonium ylide, see: Ochiai, M.; Tada, N.; Murai, K.;
Goto, S.; Shiro, M. Synthesis and Characterization of Bromonium
Ylides and Their Unusual Ligand Transfer Reactions with
N-Heterocycles. J. Am. Chem. Soc. 2006, 128, 9608–9609.
5. Tolstaya, T. P.; Demkina, I. I.; Grushin, V. V.; Vanchikov, A. N.
Nucleophilic
Substitution
in
Diphenylbromonium
and
Diphenylchloronium Salts. J. Org. Chem. USSR 1989, 25, 2305–
2310.
6. Hansch, C.; Leo, A.; Taft, R. W. A Survey of Hammett Substituent
Constants and Resonance and Field Parameters. Chem. Rev. 1991,
91, 165–195. (b) Grushin, V. V. Carboranylhalonium Ions: from
19. N-Arylation of pyridine derivatives cannot be achieved by using
diazonium salts because of the radicalic arylation of pyridine rings.
Abramovitch, R. A.; Saha, J. G. Arylations Using Diazonium
Striking Reactivity to
a Unified Mechanistic Analysis of Polar
Reactions of Diarylhalonium Compounds. Acc. Chem. Res. 1992, 25,
529–536. (c) Grushin, V. V.; Demkina, I. I.; Tolstaya, T. P.; Galakhov,
M. V.; Bakhmutov, V. I. The Electronic Effects of
Phenylhalogenonium and 9-m-Carboranylhalogenonium Groups.
Nucleophilic Substitution in Halogenonium Salts of the Carbaborane
and Aromatic Series. Organomet. Chem. USSR 1989, 2, 373–378.
7. Okuyama, T.; Takino, T.; Sueda, T.; Ochiai, M. Solvolysis of
Cyclohexenyliodonium Salt, a New Precursor for the Vinyl Cation:
Remarkable Nucleofugality of the Phenyliodonio Group and
Evidence for Internal Return from an Intimate Ion-molecule Pair. J.
Am. Chem. Soc. 1995, 117, 3360–3367. (b) Miyamoto, K. Synthesis
of Hypervalent Organo-λ3-bromanes and Their Reactions by Using
Leaving Group Ability of λ3-Bromanyl Group. YAKUGAKU ZASSHI
2014, 134, 1287–1300. (c) Miyamoto, K.; Iwasaki, S.; Doi, R.; Ota,
T.; Kawano, Y.; Yamashita, J.; Sakai, Y.; Tada, N.; Ochiai, M.; Hayashi,
S.; Nakanishi, W.; Uchiyama, M. Mechanistic Studies on the
Generation and Properties of Superelectrophilic Singlet Carbenes
from Bis(perfluoroalkanesulfonyl)bromonium Ylides. J. Org. Chem.
2016, 81, 3188–3198.
Tetrafluoroborate and Pyridine:
A Convenient Source of Aryl
Radicals. Tetrahedron 1965, 21, 3297–3303. We also examined the
mesitylation of pyridazine with 4a-BArf4 but without success (Scheme
S2 in Supporting Information).
20. N-Mesitylpyridinium salt has found a synthetic use as a precursor of
stable pyridylidene-type carbene: (a) Hata, K.; Segawa, Y.; Itami, K.
1,3,5-Triaryl 2-Pyridylidene: Base-promoted Generation and
Complexation. Chem. Commun. 2012, 48, 6642–6644. (b) Vivancos,
Á.; Segarra, C.: Albrecht, M. Mesoionic and Related Less
Heteroatom-stabilized N-Heterocyclic Carbene Complexes:
Synthesis, Catalysis, and Other Applications. Chem. Rev. 2018, 118,
9493.
21. Recently, our group and Ciufolini et al. have independently
established the aryl transfer (iodonium metathesis) reaction of
diaryl-λ3-iodane 1-OTf to a wide range of iodoarenes at elevated
temperature (>85 °C). However, this aryl transfer reaction never
occurs with bromo/chloroarenes. (a) Masumoto, Y.; Miyamoto, K.;
Iuchi, T.; Ochiai, M.; Hirano, K.; Saito, T.; Wang, C.; Uchiyama, M.
Mechanistic Study on Aryl-exchange Reaction of Diaryl-λ3-iodane
with Aryl Iodide. J. Org. Chem. 2018, 83, 289–295. (b) Kasahara, T.;
Jang, Y. J.; Racicot, L.; Panagopoulos, D.; Liang, S. H.; Ciufolini, M. A.
Iodonium Metathesis Reactions. Angew. Chem., Int. Ed. 2014, 53,
9637–9639. (c) Racicot, L.; Ciufolini, M. A. Iodonium Metathesis
Reactions of Unreactive Aryl Iodides. Tetrahedron 2017, 73, 7067–
7072.
8. (a) Sandin, R. B.; Hay, A. S. Stable Bromonium and Chloronium Salts.
J. Am. Chem. Soc. 1952, 74, 274–275. (b) Nesmeyanov A. N.;
Tolstaya T. P. Diphenylchloronium Salts. Dokl. Akad. Nauk SSSR
1955, 105, 94–95. (c) Olah, G. A.; Sakakibara, T.; Asensio, G.
Onium Ions. 17. Improved Preparation, Carbon-13 Nuclear Magnetic
Resonance Structural Study, and Nucleophilic Nitrolysis (Nitrative
Cleavage) of Diarylhalonium Ions. J. Org. Chem. 1978, 43, 463–468.
(d) Shchepina, N. E.; Nefedov, V. D.; Toropova, M. A.; Avrorin, V.
V.; Lewis, S. B.; Mattson, B. Ion-molecular Reactions of Free
Phenylium Ions, Generated by Tritium β-Decay with Bidentate
Arenes. Tetrahedron Lett. 2000, 41, 25–27. (e) Grushin, V. V.;
Kantor, M. M.; Tolstaya, T. P.; Shcherbina, T. M. Arylation of Anions
with Diarylhalonium Fluoroborates under Conditions of Interphase
Catalysis. Bull. Acad. Sci. USSR, Div. Chem. Sci. 1984, 33, 2130–
2135. (f) German, L. S.; Delyagina, N. I.; Vanchikov, A. N.; Tolstaya,
T. P. Phenylation of Fluorine-containing C-, O- and N-Anions by
Diphenylhalonium Tetrafluoroborides. Bull. Acad. Sci. USSR, Div.
Chem. Sci. 1989, 38, 174–176. (g) Gruskii, M. E.; Ptitsyna, O. A.;
Reutov, O. A. Reaction of Diphenylchloronium and
Diphenylbromonium Fluoroborates with Strong Electron Donors. Izv.
Akad. Nauk SSSR, Ser. Khim. 1973, 1, 192–193. (h) Nesmeyanov, A.
N.; Makarova, L. G.; Tolstaya, T. P. Heterolytic Decomposition of
22. For reported trivalent fluoronium salts, see: (a) Struble, M. D.; Scerba,
M. T.; Siegler, M.; Lectka, T. Evidence for a Symmetrical Fluoronium
Ion in Solution. Science, 2013, 340, 57–60. (b) Pitts, C. R.; Holl, M.
G.; Lectka T. Spectroscopic Characterization of
a
[C–F–C]+
Fluoronium Ion in Solution. Angew. Chem. Int. Ed. 2018, 57, 1924–
1927. (c) Shchepina, N. E.; Nefedov, V. D.; Toropova, M. A.; Badun,
G. A.; Avrorin, V. V.; Fedoseev, V. M. Effect of the Structure of
Substituent in the Substrate Molecule on Nuclear-Chemical Synthesis
of Halonium Compounds. Radiochemistry 2002, 44, 378–379.
23. (a) Ochiai, M.; Yamamoto, S.; Suefuji, T.; Chen, D.-W.
Stereoselective Synthesis of (Z)-Enethiols and Their Derivatives:ꢀ
Vinylic SN2 Reaction of (E)-Alkenyl(phenyl)-λ3-iodanes with
Thioamides. Org. Lett. 2001, 3, 2753–2756. (b) Ochiai, M.;
Yamamoto, S. Vinyl-λ3-iodanes Act as Efficient Sulfur Atom
Acceptors: Vinylic SN2-based Strategy for Conversion of Tertiary
Thioamides to Amides. Chem. Commun. 2002, 2802–2803.
Onium
Compounds
(Diphenyl
Halogenonium
and
Triphenyloxonium Salts). Tetrahedron 1957, 1, 145–157. (i) Ochiai,
M.; Tada, N.; Okada, T.; Sota, A.; Miyamoto, K. Thermal and
Catalytic Transylidations between Halonium Ylides and Synthesis
and Reaction of Stable Aliphatic Chloronium Ylides. J. Am. Chem.
Soc. 2008, 130, 2118–2119.
24. (a) Ochiai, M.; Hirobe, M.; Miyamoto, K. Silver Technology for
Stabilization of Simple (Z)-Enethiols:ꢀ Stereoselective Synthesis and
Reaction of Silver (Z)-Enethiolates. J. Am. Chem. Soc. 2006, 128,
9046–9047. (b) Miyamoto, K.; Hirobe, M.; Uchiyama, M.; Ochiai, M.
Stereoselective Synthesis and Reaction of Gold(I) (Z)-Enethiolates.
Chem. Commun. 2015, 51, 7962–7965.
9. (a) Balz, G.; Schiemann, G. Über Aromatische Fluorverbindungen, I.:
Ein Neues Verfahren zu Ihrer Darstellung. Ber. 1927, 60, 1186–1190.
(b) Li, J.-J.; Corey, E. J. Name Reactions for Functional Group
Transformations; Wiley: Hoboken, NJ, 2007; p. 552.
10. (a) Krossing, I.; Raabe, I. Noncoordinating Anions—Fact or Fiction?
A Survey of Likely Candidates. Angew. Chem., Int. Ed. 2004, 43,
2066–2090. (b) Strauss, S. H. The Search for Larger and More
Weakly Coordinating Anions. Chem. Rev. 1993, 93, 927–942.
11. Shoji, Y.; Tanaka, N.; Mikami, K.; Uchiyama, M.; Fukushima, T. A
Two-coordinate Boron Cation Featuring C–B+–C Bonding. Nat.
Chem. 2014, 6, 498–503.
12. (a) Douvris, C.; Michl, J. Update
1 of: Chemistry of the
Carba-closo-dodecaborate(–) Anion, CB11H12–. Chem. Rev. 2013,
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