Organic Letters
Letter
(e) He, W.; Zhang, R.; Cai, M. A Highly Efficient Heterogeneous
Copper-Catalyzed Chlorodeboronation of Arylboronic Acids Leading
to Chlorinated Arenes. RSC Adv. 2017, 7, 764−770.
Profiles, Auto-catalysis and Disproportionation. J. Am. Chem. Soc.
2016, 138, 9145−9157.
(12) For example, see: (a) Butters, M.; Harvey, J. N.; Jover, J.;
Lennox, A. J. J.; Lloyd-Jones, G. C.; Murray, P. M. Aryl
Trifluoroborates in Suzuki−Miyaura Coupling: The Roles of
Endogenous Aryl Boronic Acid and Fluoride. Angew. Chem., Int. Ed.
2010, 49, 5156−5160. (b) Molloy, J. J.; Clohessy, T. A.; Irving, C.;
Anderson, N. A.; Lloyd-Jones, G. C.; Watson, A. J. B. Chemoselective
Brown Oxidation of Aryl Organoboron Systems Enabled by Boronic
Acid-selective Phase Transfer. Chem. Sci. 2017, 8, 1551−155.
(c) Molloy, J. J.; Seath, C. P.; West, M. J.; McLaughlin, C.;
Fazakerley, N. J.; Kennedy, A. R.; Nelson, D. J.; Watson, A. J. B.
Interrogating Pd(II) Anion Metathesis using a Bifunctional Chemical
Probe: A Transmetalation Switch. J. Am. Chem. Soc. 2018, 140, 126−
130.
(5) For selected examples, see: (a) Preshlock, S.; Calderwood, S.;
Verhoog, S.; Tredwell, M.; Huiban, M.; Hienzsch, A.; Gruber, S.;
Wilson, T. C.; Taylor, N. J.; Cailly, T.; Schedler, M.; Collier, T. L.;
Passchier, J.; Smits, R.; Mollitor, J.; Hoepping, A.; Mueller, M.;
Genicot, C.; Mercier, J.; Gouverneur, V. Enhanced Copper-Mediated
18F-Fluorination of Aryl Boronic Esters Provides Eight Radiotracers
for PET Applications. Chem. Commun. 2016, 52, 8361−8364.
(b) Wilson, T. C.; McSweeney, G.; Preshlock, S.; Verhoog, S.;
Tredwell, M.; Cailly, T.; Gouverneur, V. Radiosynthesis of SPECT
Tracers via a Copper Mediated 123I Iodination of (Hetero)aryl Boron
Reagents. Chem. Commun. 2016, 52, 13277−13280. (c) Taylor, N. J.;
Emer, E.; Preshlock, S.; Schedler, M.; Tredwell, M.; Verhoog, S.;
Mercier, J.; Genicot, C.; Gouverneur, V. Derisking the Cu-Mediated
18F-Fluorination of Heterocyclic Positron Emission Tomography
Radioligands. J. Am. Chem. Soc. 2017, 139, 8267−8276.
(13) Matteson, D. S.; Liedtke, J. D. Mechanisms of Deborono-
bromination. J. Am. Chem. Soc. 1965, 87, 1526−1531.
(14) Lorand, J.; Edwards, J. O. Polyol Complexes and Structure of
the Benzeneboronate Ion. J. Org. Chem. 1959, 24, 769−774.
(15) (a) Vankar, Y. D.; Kumaravel, G. N-Chlorosuccinimide/
Sodium Iodide: A Convenient Source of N-Iodosuccinimide.
Synthesis of α-Iodo Carbonyl Compounds and trans-1,2-Iodoacetates.
Tetrahedron Lett. 1984, 25, 233−236. (b) Youfeng, H.; Coenen, H.
(6) For a review of metal-free organoboron ipso-substitution, see:
Zhu, C.; Falck, J. R. Transition Metal-Free ipso-Functionalization of
Arylboronic Acids and Derivatives. Adv. Synth. Catal. 2014, 356,
2395−2410.
(7) (a) Kuivila, H. G.; Easterbrook, E. K. Kinetics of the
Brominolysis of Benzeneboronic Acid in Aqueous Acetic Acid
Solution. J. Am. Chem. Soc. 1951, 73, 4629−4632. (b) Kuivila, H.
G.; Hendrickson, A. R. Electrophilic Displacement Reactions. II.
Rates of Brominolysis of Substituted Benzeneboronic Acids. J. Am.
Chem. Soc. 1952, 74, 5068−5070. (c) Kuivila, H. G.; Williams, R. M.
Electrophilic Displacement Reactions. V. Kinetics of the Iodinolysis of
p-Methoxybenzeneboronic Acid. J. Am. Chem. Soc. 1954, 76, 2679−
2682.
(8) (a) Vantourout, J. C.; Li, L.; Bendito-Moll, E.; Chabbra, S.;
Arrington, K.; Bode, B. E.; Isidro-Llobet, A.; Kowalski, J. A.; Nilson,
M.; Wheelhouse, K.; Woodard, J. L.; Xie, S.; Leitch, D. C.; Watson, A.
J. B. Mechanistic Insight Enables Practical, Scalable, Room Temper-
ature Chan-Lam N-Arylation of N-Aryl Sulfonamides. ACS Catal.
2018, 8, 9560−9566. (b) Vantourout, J. C.; Miras, H. N.; Isidro-
Llobet, A.; Sproules, S.; Watson, A. J. B. Spectroscopic Studies of the
Chan-Lam Amination: A Mechanism-inspired Solution to Boronic
Ester Reactivity. J. Am. Chem. Soc. 2017, 139, 4769−4779.
(c) Vantourout, J. C.; Law, R. P.; Isidro-Llobet, A.; Atkinson, S. J.;
Watson, A. J. B. Chan-Evans-Lam Amination of Boronic Acid Pinacol
(BPin) Esters: Overcoming the Aryl Amine Problem. J. Org. Chem.
2016, 81, 3942−3950.
(9) (a) Cant, A. A.; Champion, S.; Bhalla, R.; Pimlott, S. L.;
Sutherland, A. Nickel-Mediated Radioiodination of Aryl and
Heteroaryl Bromides: Rapid Synthesis of Tracers for SPECT Imaging.
Angew. Chem., Int. Ed. 2013, 52, 7829−7832. (b) Racys, D. T.; Sharif,
S. A. I.; Pimlott, S. L.; Sutherland, A. Silver(I)-Catalyzed Iodination of
Arenes: Tuning the Lewis Acidity of N-Iodosuccinimide Activation. J.
Org. Chem. 2016, 81, 772−780. (c) Sloan, N. L.; Luthra, S. K.;
McRobbie, G.; Pimlott, S. L.; Sutherland, A. A One-Pot Radio-
iodination of Aryl Amines via Stable Diazonium Salts: Preparation of
125I-Imaging Agents. Chem. Commun. 2017, 53, 11008−11011.
(d) Webster, S.; O’Rourke, K. M.; Fletcher, C.; Pimlott, S. L.;
Sutherland, A.; Lee, A.-L. Rapid Iododeboronation with and without
Gold Catalysis: Application to Radiolabelling of Arenes. Chem. - Eur.
J. 2018, 24, 937−943.
̈
H.; Petzold, G.; Stocklin, G. A Comparative Study of Radioiodination
of Simple Aromatic Compounds via N-Halosuccinimides and
Chloramine-T in TFAA. J. Labelled Compd. Radiopharm. 1982, 19,
807−819.
(16) (a) Zhang, H.; Huang, R.; Pillarsetty, N.; Thorek, D. L. J.;
Vaidyanathan, G.; Serganova, I.; Blasberg, R. G.; Lewis, J. S. Synthesis
and Evaluation of 18F-Labeled Benzylguanidine Analogs for targeting
the Human Norepinephrine Transporter. Eur. J. Nucl. Med. Mol.
Imaging 2014, 41, 322−332. (b) Sharp, S. E.; Trout, A. T.; Weiss, B.
D.; Gelfand, M. J. MIBG in Neuroblastoma Diagnostic Imaging and
Therapy. Radiographics 2016, 36, 258−278.
(17) Zmuda, F.; Malviya, G.; Blair, A.; Boyd, M.; Chalmers, A. J.;
Sutherland, A.; Pimlott, S. L. Synthesis and Evaluation of a
Radioiodinated Tracer with Specificity for Poly(ADP-ribose)
Polymerase-1 (PARP-1) in Vivo. J. Med. Chem. 2015, 58, 8683−8693.
(18) Dobritzsch, D.; Ricagno, S.; Schneider, G.; Schnackerz, K. D.;
Lindqvist, Y. Crystal Structure of the Productive Ternary Complex of
Dihydropyrimidine Dehydrogenase with NADPH and 5-Iodouracil. J.
Biol. Chem. 2002, 277, 13155−13166.
(19) (a) Lan, X.; Liu, Y.; He, Y.; Wu, T.; Zhang, B.; Gao, Z.; An, R.;
Zhang, Y. Autoradiography Study and SPECT Imaging of Reporter
Gene HSV1-TK Expression in Heart. Nucl. Med. Biol. 2010, 37, 371−
380. (b) Bettegowda, C.; Foss, C. A.; Cheong, I.; Wang, Y.; Diaz, L.;
Agrawal, N.; Fox, J.; Dick, J.; Dang, L. H.; Zhou, S.; Kinzler, K. W.;
Vogelstein, B.; Pomper, M. G. Imaging Bacterial Infections with
Radiolabeled 1-(2’-Deoxy-2’-fluoro-β-D-arabinofuranosyl)-5-iodoura-
cil. Proc. Natl. Acad. Sci. U. S. A. 2005, 102, 1145−1150.
(10) Kuivila, H. G.; Reuwer, J. F., Jr.; Mangravite, J. A. Electrophilic
Displacement Reactions. XVI. Metal Ion Catalysis in the Proto-
deboronation of Areneboronic Acids. J. Am. Chem. Soc. 1964, 86,
2666−2670.
(11) For selected studies of protodeboronation, see: (a) Cox, P. A.;
Reid, M.; Leach, A. G.; Campbell, A. D.; King, E. J.; Lloyd-Jones, G.
C. Base-catalyzed Aryl-B(OH)2 Protodeboronation Revisited: From
Concerted Proton-Transfer to Liberation of a Transient Aryl Anion. J.
Am. Chem. Soc. 2017, 139, 13156−13165. (b) Cox, P. A.; Leach, A.
G.; Campbell, A. D.; Lloyd-Jones, G. C. Protodeboronation of
Heteroaromatic, Vinyl and Cyclopropyl Boronic Acids: pH-rate
E
Org. Lett. XXXX, XXX, XXX−XXX