Spirocyclic Nitroxides as Versatile Tools in Modern Natural Sciences: From Synthesis to Applications. Part I. Old and New Synthetic Approaches to Spirocyclic Nitroxyl Radicals
Abstract
:1. Introduction
2. Piperidine Nitroxide Radicals (TEMPO Type)
3. Benzoannelated Derivatives of Piperidine-Type SNRs
3.1. SNRs of 1,2,3,4-Tetrahydroquinolines Series
3.2. SNRs of the 10H,10′H-9,9′-Spirobi[acridine] Series
4. Piperazine- and Morpholine-Type SNRs
5. 2,5-Dihydropyrrole (3-Pyrroline)- and Pyrrolidine (PROXYL)-Type SNRs
6. 2,5-Dihydroimidazole (3-Imidazoline)-Type SNRs
7. 4,5-Dihydroimidazole (2-Imidazoline)-Type SNRs
8. Imidazolidine-Type SNRs
9. Oxazolidine (DOXYL) SNRs
10. SNRs of Other Types
11. Conclusions
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Conflicts of Interest
Abbreviations
AMUPol | (15-{[(7-Oxyl-3,11-dioxa-7-azadispiro[5.1.5.3]hexadec-15-yl)carbamoyl][2-(2,5,8,11-tetraoxatridecan-13-ylamino)}-[3,11-dioxa-7-azadispiro[5.1.5.3]hexadec-7-yl])oxidanyl; |
BCEDIPPA | Bis(2-cyanoethyl)-N,N-diisopropylphosphoramidite; |
bcTol | [Bis(spirocyclohexyl-TEMPO-alcohol)urea]; |
BINAP | 2,2′-Bis(diphenylphosphino)-1,1′-binaphthyl; |
BMS | Borane dimethylsulfide; |
Boc2O | Di-tert-butyl dicarbonate, (ButOCO)2O; |
bTbK | Bis-TEMPO-bis-ketal; |
BTC | Bis(trichloromethyl) carbonate (Triphosgene); |
BTEAC | Benzyltriethylammonium chloride; |
BTT | 5-(Benzylthio)-1H-tetrazole; |
m-CPBA | meta-Chloroperoxybenzoic acid; |
CDI | 1,1′-Carbonyldiimidazole; |
CSA | Camphorsulfonic acid, (7,7-dimethyl-2-oxobicyclo[2.2.1]heptan-1-yl)methanesulfonic acid; |
cyolyl-TOTAPOL | [Spirocyclohexanolyl-1-(TEMPO-4-oxy)-3-(TEMPO-4-amino)propan-2-ol]; |
DBU | 1,8-Diazabicyclo[5.4.0]undec-7-ene; |
DCC | N,N′-Dicyclohexylcarbodiimide; |
DCM | Dichloromethane; |
DDQ | 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone; |
DEER | Double electron-electron resonance; |
DIBAL-H | Diisobutylaluminium hydride; |
DIPEA | N,N-Diisopropylethylamine (Hünig’s base); |
DMAP | 4-Dimethylaminopyridine; |
DMDO | Dimethyldioxirane; |
DME | Dimethoxyethane; |
DMEDA | N,N′-Dimethylethylenediamine; |
2,6-DMP | 2,6-Dimethoxypyridine; |
DMP | Dess–Martin periodinane (3-Oxo-1,3-dihydro-1λ5,2-benziodoxole-1,1,1-triyl triacetate); |
DMT-MM | 4-(4,6-Dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride; |
DOXYL | Oxazolidine-3-oxyl; |
EDCI | 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide; |
EDTA-Na2 | Ethylenediaminetetraacetic acid, disodium salt; |
Fmoc-Cl | 9-Fluorenylmethoxycarbonyl chloride; |
Fmoc-OSu | N-(9-Fluorenylmethoxycarbonyloxy)succinimide; |
GSH | Glutathione; |
HAK | 2-Hydroxylaminoketones, R1-CO-CR2R3-NHOH; |
HFIP | 1,1,1,3,3,3-Hexafluoro-2-propanol; |
HOBt | 1-Hydroxybenzotriazole; |
KN | Kynurenine, (S)-2-Amino-4-(2-aminophenyl)-4-oxo-butanoic acid; |
LAH | Lithium aluminium hydride, LiAlH4; |
LVT-reagent | Low valent titanium species; |
MEM-Cl | 2-Methoxyethoxymethyl chloride; |
MTO | Methyltrioxorhenium, CH3ReO3; |
MS | Molecular sieves; |
NBS | N-Bromosuccinimide; |
NHS | N-Hydroxysuccinimide; |
NMM | N-Methylmorpholine; |
ORCA | Organic radical contrast agent; |
PCC | Pyridinium chlorochromate; |
PivOH | Pivalic acid; |
PROXYL | Pyrrolidine-1-oxyl; |
PTSA | p-Toluenesulfonic acid, TsOH; |
PyPol | (15-{[(7-Oxyl-3,11-dioxa-7-azadispiro[5.1.5.3]hexadec-15-yl)carbamoyl]amino}-[3,11-dioxa-7-azadispiro[5.1.5.3]hexadec-7-yl])oxidanyl); |
Ra-Ni | Raney nickel; |
SDSL | Site-directed spin labeling; |
TBAF | Tetra-n-butylammonium fluoride; |
TBAHS | Tetrabutylammonium hydrogen sulfate; |
TBDMS | tert-Butyldimethylsilyl; |
TBTA | Tris((1-benzyl-4-triazolyl)methyl)amine; |
TEA | Triethylamine; |
TEKPOL | Bis-phenylcyclohexyl-TEMPO-bis-ketal; |
TEMPO | 2,2,6,6-Tetramethylpiperidine-1-oxyl; |
TEMPOL | 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl; |
TEMPON | 2,2,6,6-Tetramethyl-4-oxypiperidine-1-oxyl; |
TMEDA | N,N,N′,N′-Tetramethylethylenediamine; |
TMG | 1,1,3,3-Tetramethylguanidine; |
TMP | 2,2,6,6-Tetramethylpiperidine; |
TMSCN | Trimethylsilyl cyanide; |
TMSOTf | Trimethylsilyl trifluoromethanesulfonate, CF3SO3SiMe3; |
TMSSPh | Trimethyl(phenylthio)silane, PhS-SiMe3; |
TOAC | 2,2,6,6-Tetramethylpiperidine-1-oxyl-4-amino-4-carboxylic acid; |
TosMIC | Toluenesulfonylmethyl isocyanide; |
UHP | Urea hydrogen peroxide |
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Entry | Ketone | 6, % | 7, % | 8, % |
---|---|---|---|---|
1 | 4 | 37 | 59 | |
2 | 25 | 63 | 12 | |
3 | 18 | 22 | 0 | |
4 | 14 | 62 | 14 | |
5 | 21 | 46 | 33 | |
6 | 18 | 82 | 0 | |
7 | 28 | 72 | 0 | |
8 | 84 | 16 | 0 | |
9 | 34 | 66 | 0 |
329, 330 | R1 | R2 | R3 | R4 | Yield of Amine 329, % | Yield of SNR 330, % |
---|---|---|---|---|---|---|
a | (CH2)5 | (CH2)5 | 86 | 78 | ||
b | (CH2)5 | H | n-C3H7 | 76 | nonradical | |
c | CH3 | CH3 | (CH2)5 | 90 | 89 | |
d | (CH2)5 | (CH2)4 | 70 | ND | ||
e | (CH2)5 | H | n–C11H23 | 24 | nonradical | |
f | (CH2)5 | H | Ph | 86 | nonradical | |
g | (CH2)5 | CH3 | 3-Pyridyl | 67 | ND | |
h | (CH2)5 | 4,4-TMP | 40 | ND | ||
i | (CH2)5 | 4,4-TEMPO | 34 | 16 | ||
j | 4,4-TMP | H | CCl3 | 88 | nonradical | |
k | 4,4-TMP | H | p-Cl-C6H4 | 69 | nonradical | |
l | 4,4-TEMPO | H | n–C3H7 | 61 | nonradical | |
m | 4,4-TEMPO | (CH2)5 | 45 | 81 | ||
n | 4,4-TEMPO | H | Ph | 64 | nonradical | |
o | 4,4-TEMPO | H | o-CH3-C6H4 | 88 | nonradical | |
p | 4,4-TEMPO | H | p–CH3O-C6H4 | 81 | nonradical | |
q | 4,4-TEMPO | 4,4-TEMPO | 24 | ND | ||
r | H | Ph | (CH2)5 | 40 | nonradical | |
s | CH3 | Ph | (CH2)5 | 40 | ND | |
t | 2–CH3-Cyclohexyl | 2–CH3-Cyclohexyl | 36 | 67 |
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Zaytseva, E.V.; Mazhukin, D.G. Spirocyclic Nitroxides as Versatile Tools in Modern Natural Sciences: From Synthesis to Applications. Part I. Old and New Synthetic Approaches to Spirocyclic Nitroxyl Radicals. Molecules 2021, 26, 677. https://doi.org/10.3390/molecules26030677
Zaytseva EV, Mazhukin DG. Spirocyclic Nitroxides as Versatile Tools in Modern Natural Sciences: From Synthesis to Applications. Part I. Old and New Synthetic Approaches to Spirocyclic Nitroxyl Radicals. Molecules. 2021; 26(3):677. https://doi.org/10.3390/molecules26030677
Chicago/Turabian StyleZaytseva, Elena V., and Dmitrii G. Mazhukin. 2021. "Spirocyclic Nitroxides as Versatile Tools in Modern Natural Sciences: From Synthesis to Applications. Part I. Old and New Synthetic Approaches to Spirocyclic Nitroxyl Radicals" Molecules 26, no. 3: 677. https://doi.org/10.3390/molecules26030677