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A Pd-catalyzed process and conditions under photoredox catalysis (both proceeding through complex multistep mechanisms) are known. These catalytic processes allow for much milder reaction conditions to be used (100 °C for Pd catalysis, ambient temperature for photoredox).
343:
Harvey, J. N.; Jover, J.; Lloyd-Jones, G. C.; Moseley, J. D.; Murray, P. M.; Renny, J. S. (2009). "The Newman–Kwart
Rearrangement of O-Aryl Thiocarbamates: Substantial Reduction in Reaction Temperatures through Palladium Catalysis".
383:
Lloyd-Jones, G. C.; Moseley, J. D.; Renny, J. S. (2008). "Mechanism and
Application of the Newman-Kwart O→S Rearrangement of O-Aryl Thiocarbamates".
308:
70:
610:
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Burns, Matthew; Lloyd-Jones, G. C.; Moseley, J. D.; Renny, J. S. (2010). "The
Molecularity of the Newman−Kwart Rearrangement".
473:
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63:
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412:
Newman, M. S.; Karnes, H. A. (1966). "The
Conversion of Phenols to Thiophenols via Dialkylthiocarbamates".
213:
88:
39:
171:). The enthalpy of activation for this transition state is generally quite high for typical substrates (Δ
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Kwart, H.; Evans, E. R. (1966). "The Vapor Phase
Rearrangement of Thioncarbonates and Thioncarbamates".
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295:. Topics in Current Chemistry. Vol. 275. Springer Berlin / Heidelberg. pp. 131–161.
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536:"Ambient-Temperature Newman–Kwart Rearrangement Mediated by Organic Photoredox Catalysis"
134:. The Newman–Kwart reaction represents a useful synthetic tool for the preparation of
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175:~ 30 to 40 kcal/mol), necessitating high reaction temperatures (200 to 300 °C, Ph
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The Newman–Kwart rearrangement is an important prelude to the synthesis of
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Thione–Thiol
Rearrangement: Miyazaki–Newman–Kwart Rearrangement and Others
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Melvin S. Newman; Frederick W. Hetzel (1971). "Thiophenols from
Phenols:
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to around 250 °C causes it undergo Newman–Kwart rearrangement to an
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Perkowski, Andrew J.; Cruz, Cole L.; Nicewicz, David A. (2015-12-23).
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159:. It is generally believed to be a concerted process, proceeding
244:). Alkaline hydrolysis or similar cleavage yields a thiophenol (
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Zonta, C.; De Lucchi, O.; Volpicelli, R.; Cotarca, L. (2007).
212:) is deprotonated with a base followed by treatment with a
167:(rather than a two-step process passing through a discrete
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and Harold Kwart. The reaction is a manifestation of the
507:Jacobsen, Heiko; Donahue, James P. (2011-02-05).
126:. The reaction is named after its discoverers,
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196:Use for preparation of thiophenols
155:The Newman–Kwart rearrangement is
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19:Newman-Kwart rearrangement
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56:newman-kwart-rearrangement
179:O as solvent or neat).
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591:10.15227/orgsyn.051.0139
611:Rearrangement reactions
163:a four-membered cyclic
399:10.1055/s-2008-1032179
359:10.1002/anie.200903908
214:thiocarbamoyl chloride
89:rearrangement reaction
40:Rearrangement reaction
347:Angew. Chem. Int. Ed.
272:Chapman rearrangement
224:-aryl thiocarbamate (
169:reactive intermediate
128:Melvin Spencer Newman
28:Melvin Spencer Newman
552:10.1021/jacs.5b11800
267:Smiles rearrangement
546:(50): 15684–15687.
455:10.1021/jo01340a015
427:10.1021/jo01350a023
100:-aryl thiocarbamate
575:2-Naphthalenethiol
486:10.1021/jo1014382
480:(19): 6347–6353.
421:(12): 3980–3984.
353:(41): 7612–7615.
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114:atom to the
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71:RXNO:0000412
66:ontology ID
46:Identifiers
24:Named after
228:). Heating
202:thiophenols
605:Categories
579:Org. Synth
278:References
136:thiophenol
93:aryl group
560:0002-7863
386:Synthesis
319:0340-1022
151:Mechanism
110:from the
494:20812755
367:19746383
327:23605512
261:See also
108:migrates
585:: 139.
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236:-aryl
206:phenol
116:sulfur
112:oxygen
95:of an
556:ISSN
490:PMID
391:2008
363:PMID
323:PMID
315:ISSN
305:ISBN
204:. A
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587:doi
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