Page 17 of 18
The Journal of Organic Chemistry
stereoselective and electrocatalytic synthesis of diisoeugenol.
Chem. Commun. 2018, 54, 2771–2773.
(32) Nutting, J. E.; Rafiee, M.; Stahl, S. S. Tetramethylpiperidine
N-Oxyl (TEMPO), Phthalimide N-Oxyl (PINO), and Related N-Oxyl
Species: Electrochemical Properties and Their Use in Electrocata-
lytic Reactions. Chem. Rev. 2018, 118, 4834–4885.
(33) Savéant, J.-M. Molecular catalysis of electrochemical reac-
tions. Mechanistic aspects. Chem. Rev. 2008, 108, 2348–2378.
(34) Ackermann, L. Metalla-electrocatalyzed C-H Activation by
Earth-Abundant 3d Metals and Beyond. Acc. Chem. Res. 2020, 53,
84–104.
(35) The electron-catalyzed SRN1-reactions (see refs. 16 and 17)
constitute a particularly well studied system.
(36) In principle, another version of TS-3 containing one S,S-
and one O,O-acetal unit is also conceivable.
1
2
3
4
5
6
7
8
(14) Park, Y. S.; Little, R. D. Redox electron-transfer reactions:
Electrochemically mediated rearrangement, mechanism, and a to-
tal synthesis of daucene. J. Org. Chem. 2008, 73, 6807–6815.
(15) Broese, T.; Roesel, A. F.; Prudlik, A.; Francke, R. An Electro-
catalytic Newman-Kwart-type Rearrangement. Org. Lett. 2018, 20,
7483–7487.
(16) Amatore, C.; Pinson, J.; Savéant, J. M.; Thiebault, A. Electron
transfer induced reactions. Electrochemically stimulated aromatic
nucleophilic substitution in organic solvents. J. Am. Chem. Soc.
1982, 104, 817–826.
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) Pinson, J.; Savéant, J.-M. Electrolytic reduction of p-bromo-
benzophenone in the presence of benzenethiolate: an electrochem-
ically catalysed aromatic nucleophilic substitution. J. Chem. Soc.,
Chem. Commun. 1974, 933–934.
(37) Gilday, J. P.; Lenden, P.; Moseley, J. D.; Cox, B. G. The New-
man-Kwart rearrangement: a microwave kinetic study. J. Org.
Chem. 2008, 73, 3130–3134.
(18) Lloyd-Jones, G. C.; Moseley, J.; Renny, J. Mechanism and Ap-
plication of the Newman-Kwart O→S Rearrangement of O-Aryl Thi-
ocarbamates. Synthesis 2008, 661–689.
(19) Newman, M. S.; Karnes, H. A. The Conversion of Phenols to
Thiophenols via Dialkylthiocarbamates. J. Org. Chem. 1966, 31,
3980−3984.
(20) Zonta, C.; Lucchi, O. de; Volpicelli, R.; Cotarca, L. Thione-
thiol rearrangement: Miyazaki-Newman-Kwart rearrangement
and others. Top. Curr. Chem. 2007, 275, 131–161.
(21) Moseley, J. D.; Sankey, R. F.; Tang, O. N.; Gilday, J. P. The New-
man–Kwart rearrangement re-evaluated by microwave synthesis.
Tetrahedron 2006, 62, 4685–4689.
(22) Moseley, J. D.; Lenden, P. A high temperature investigation
using microwave synthesis for electronically and sterically disfa-
voured substrates of the Newman−Kwart rearrangement. Tetrahe-
dron 2007, 63, 4120−4125.
(23) Hoffmann, I.; Schatz, J. Microwave-mediated New-
man−Kwart rearrangement in water. RSC Adv. 2016, 6,
80692−80699.
(24) Brooker, S.; Caygill, G. B.; Croucher, P. D.; Davidson, T. C.;
Clive, D. L. J.; Magnuson, S. R.; Cramer, S. P.; Ralston, C. Y. Conver-
sion of some substituted phenols to the corresponding masked thi-
ophenols, synthesis of a dinickel(II) dithiolate macrocyclic com-
plex and isolation of some metal- and ligand-based oxidation prod-
ucts. J. Chem. Soc., Dalton Trans. 2000, 3113−3121.
(25) Harvey, J. N.; Jover, J.; Lloyd-Jones, G. C.; Moseley, J. D.; Mur-
ray, P.; Renny, J. S. The Newman−Kwart rearrangement of O-aryl
thiocarbamates: Substantial reduction in reaction temperatures
through palladium catalysis. Angew. Chem., Int. Ed. 2009, 48,
7612−7615.
(26) Perkowski, A. J.; Cruz, C. L.; Nicewicz, D. A. Ambient-Tem-
perature Newman-Kwart Rearrangement Mediated by Organic
Photoredox Catalysis. J. Am. Chem. Soc. 2015, 137, 15684–15687.
(27) The use of cerium ammonium nitrate in DMSO allows for
reaction at room temperature, see Pedersen, S. K.; Ulfkjær, A.; New-
man, M. N.; Yogarasa, S.; Petersen, A. U.; Sølling, T. I.; Pittelkow, M.
Inverting the Selectivity of the Newman-Kwart Rearrangement via
One Electron Oxidation at Room Temperature. J. Org. Chem. 2018,
83, 12000–12006.
(28) The Fe(II)/persulfate mediated NKR is carried out at tem-
peratures between 45 and 65 °C, see Gendron, T.; Pereira, R.; Abdi,
H. Y.; Witney, T. H.; Årstad, E. Iron(II)/Persulfate Mediated New-
man-Kwart Rearrangement. Org. Lett. 2020, 22, 274–278.
(29) The increased rates are usually explained by a stabilization
of the negative charge in Meisenheimer-type TS-1 by electron-
withdrawing substituents (see ref. 18).
(38) Burns, M.; Lloyd-Jones, G. C.; Moseley, J. D.; Renny, J. S. The
molecularity of the Newman-Kwart rearrangement. J. Org. Chem.
2010, 75, 6347–6353.
(39) Wang, J. Analytical Electrochemistry (3rd Edition); Wiley-
VCH, 2006.
gielch-electrochemical-simulation-software/.
(41) Chemical irreversibility of the 2t/2t•+ couple was con-
firmed by lowering the upper vertex potential to 1.50 V (prior to
the foot of the second wave). For more information, see the SI.
(42) Bard, A. J.; Faulkner, L. R. Electrochemical Methods: Funda-
mentals and Applications, 2. ed.; Wiley: New York, 2001.
(43) Hansch, C.; Leo, A.; Taft, R. W. A survey of Hammett substit-
uent constants and resonance and field parameters. Chem. Rev.
1991, 91, 165–195.
(44) Francke, R.; Little, R. D. Optimizing electron transfer medi-
ators based on arylimidazoles by ring fusion: synthesis, electro-
chemistry, and computational analysis of 2-aryl-1-methylphenan-
thro[9,10-d]dimidazoles. J. Am. Chem. Soc. 2014, 136, 427–435.
(45) Chiniforoush, S.; Cramer, C. J. Quantum Chemical Character-
ization of Factors Affecting the Neutral and Radical-Cation New-
man-Kwart Reactions. J. Org. Chem. 2019, 84, 2148–2157.
(46) Cruz, C. L.; Nicewicz, D. A. Mechanistic Investigations into
the Cation Radical Newman–Kwart Rearrangement. ACS Catal.
2019, 9, 3926–3935.
(47) Iffland, L.; Khedkar, A.; Petuker, A.; Lieb, M.; Wittkamp, F.;
van Gastel, M.; Roemelt, M.; Apfel, U.-P. Solvent-Controlled CO2 Re-
duction by a Triphos–Iron Hydride Complex. Organometallics
2019, 38, 289–299.
(48) Xue, G.; Geng, C.; Ye, S.; Fiedler, A. T.; Neese, F.; Que, L. Hy-
drogen-bonding effects on the reactivity of X-Fe(III)-O-Fe(IV)═O
(X = OH, F) complexes toward C-H bond cleavage. Inorg. Chem.
2013, 52, 3976–3984.
(49) Cismesia, M. A.; Yoon, T. P. Characterizing Chain Processes
in Visible Light Photoredox Catalysis. Chem. Sci. 2015, 6, 5426–
5434.
(50) Ruccolo, S.; Qin, Y.; Schnedermann, C.; Nocera, D. G. General
Strategy for Improving the Quantum Efficiency of Photoredox Hy-
droamidation Catalysis. J. Am. Chem. Soc. 2018, 140, 14926–14937.
(51) Streeter, I.; Wain, A. J.; Thompson, M.; Compton, R. G. In situ
electrochemical ESR and voltammetric studies on the anodic oxi-
dation of para-haloanilines in acetonitrile. J. Phys. Chem. B 2005,
109, 12636–12649.
(52) Andrieux, C. P.; Gallardo, I.; Junca, M. Mechanistic study of
the electrochemical oxidation of some aromatic amines in the pres-
ence of bases. J. Electroanal. Chem. 1993, 354, 231–241.
(53) Schmidt, W.; Steckhan, E. Über organische Elektronenüber-
trägersysteme, I. Elektrochemische und spektroskopische Unter-
suchung bromsubstituierter Triarylamin-Redoxsysteme. Chem.
Ber. 1980, 113, 577–585.
(30) Siu, J. C.; Fu, N.; Lin, S. Catalyzing Electrosynthesis: A Homo-
geneous Electrocatalytic Approach to Reaction Discovery. Acc.
Chem. Res. 2020, 53, 547–560.
(31) Francke, R.; Little, R. D. Redox catalysis in organic electro-
synthesis: Basic principles and recent developments. Chem. Soc.
Rev. 2014, 43, 2492–2521.
(54) Francke, R.; Cericola, D.; Weingarth, D.; Kötz, R.; Waldvogel,
S. R. Novel Electrolytes for Electrochemical Double Layer
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