Organic Letters
Letter
hydroxyl functional groups showed good compatibility. The
chlorine atom in products was efficiently substituted in situ
with various nucleophiles providing benzylic compounds of a
previously inaccessible substitution pattern. Finally, a mild
oxidation of the chloromethyl group was developed to access
substituted nitrobenzaldehydes.
(11) Makosza, M.; Surowiec, M.; Voskresensky, S. Synthesis of (p-
Nitroaryl)diarylmethanes via Vicarious Nucleophilic Substitution of
Hydrogen. Synthesis 2000, 2000, 1237.
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12) Ko
and Trichloromethyl-lithium. Angew. Chem., Int. Ed. Engl. 1964, 3,
13.
13) Ko
Drischel, W.; Fischer, R. H.; Flory, K.; Fro
Heinemann, H.; Hornke, I.; Merkle, H. R.; Trapp, H.; Zu
̈
brich, G.; Flory, K.; Drischel, W. Dichloromethyl-lithium
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brich, G.; Akhtar, A.; Ansari, F.; Breckoff, W. E.; Bu
hlich, H.; Goyert, W.;
ndorf, W.
̈
ttner, H.;
̈
ASSOCIATED CONTENT
Supporting Information
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S
Chemistry of Stable α-Halogenoorganolithium Compounds and the
Mechanism of Carbenoid Reactions. Angew. Chem., Int. Ed. Engl.
1
(
967, 6, 41.
14) Makosza, M.; Owczarczyk, Z. Reactions of organic anions. 161.
Dihalomethylation of nitroarenes via vicarious nucleophilic sub-
stitution of hydrogen with trihalomethyl carbanions. J. Org. Chem.
Experimental details and NMR data (PDF)
1
989, 54, 5094.
(15) Matteson, D. S.; Majumdar, D. Homologation of boronic esters
to.alpha.-chloro boronic esters. Organometallics 1983, 2, 1529.
CCDC 1906014 contains the supplementary crystallographic
bridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
(16) Matteson, D. S.; Sadhu, K. M.; Peterson, M. L. 99% Chirally
selective synthesis via pinanediol boronic esters: insect pheromones,
diols, and an amino alcohol. J. Am. Chem. Soc. 1986, 108, 810.
(
17) Beier, P.; Pastyríkova, T.; Iakobson, G. Preparation of SF5
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Aromatics by Vicarious Nucleophilic Substitution Reactions of
Nitro(pentafluorosulfanyl)benzenes with Carbanions. J. Org. Chem.
2
011, 76, 4781.
(18) Beier, P.; Pasty
pentafluorosulfanyl)benzenes via vicarious nucleophilic substitution
of hydrogen. Tetrahedron Lett. 2011, 52, 4392.
19) Pastyr kova, T.; Iakobson, G.; Vida, N.; Pohl, R.; Beier, P.
AUTHOR INFORMATION
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ríkova, T. Hydroxylation of nitro-
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ORCID
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í
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Direct Amination of Nitro(pentafluorosulfanyl)benzenes through
Vicarious Nucleophilic Substitution of Hydrogen. Eur. J. Org. Chem.
Notes
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012, 2012, 02123.
(20) Savoie, P. R.; Welch, J. T. Preparation and Utility of Organic
Pentafluorosulfanyl-Containing Compounds. Chem. Rev. 2015, 115,
The authors declare no competing financial interest.
1130.
(
21) Altomonte, S.; Zanda, M. Synthetic chemistry and biological
ACKNOWLEDGMENTS
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activity of pentafluorosulphanyl (SF ) organic molecules. J. Fluorine
Chem. 2012, 143, 57.
(22) Blaziak, K.; Danikiewicz, W.; Makosza, M. How does
nucleophilic aromatic substitution really proceed in nitroarenes?
Computational prediction and experimental verification. J. Am. Chem.
Soc. 2016, 138, 7276.
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Financial support from the Academy of Sciences of the Czech
Republic (Research Plan RVO 61388963) and the Czech
Science Foundation (18-00215J) is gratefully acknowledged.
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(
(
(
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Org. Lett. XXXX, XXX, XXX−XXX