by william schulz bechara charette/collins literature meeting november 13 th, 2012
TRANSCRIPT
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byWilliam Schulz Bechara
Charette/Collins Charette/Collins LiteratureLiterature Meeting MeetingNovember 13November 13thth, 2012, 2012
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The History of C–H Amination
¨In 1878, the structure of piperidine was still unknown, and A. W. Hofmann made attempts to add hydrogen chloride or bromine to it in the belief that the compound possessed unsaturation.¨
Wolff M. E. Chem. Rev. 1963, 63, 55. 2
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The History of C–H Amination
(a) Wolff M. E. Chem. Rev. 1963, 63, 55. (b) Hofmann, A. W. Chem. Ber. 1879, 12, 984.
¨Hofmann made the surprising discovery that […] a tertiary amine was obtained, and this product was later shown to be octahydroindolizine.¨
¨In 1878, the structure of piperidine was still unknown, and A. W. Hofmann made attempts to add hydrogen chloride or bromine to it in the belief that the compound possessed unsaturation.¨
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The History of C–H Amination
(a) Wolff M. E. Chem. Rev. 1963, 63, 55. (b) Hofmann, A. W. Chem. Ber. 1879, 12, 984.
¨In 1878, the structure of piperidine was still unknown, and A. W. Hofmann made attempts to add hydrogen chloride or bromine to it in the belief that the compound possessed unsaturation.¨
¨Hofmann made the surprising discovery that […] a tertiary amine was obtained, and this product was later shown to be octahydroindolizine.¨
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Isolation of Intermediates
Wolff M. E. Chem. Rev. 1963, 63, 55. 3
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Isolation of Intermediates
Wolff M. E. Chem. Rev. 1963, 63, 55. 3
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Hofmann–Löffler–Freytag Reaction
¨In 1909, K. Löffler and C. Freytag extended the scope of this transformation and demonstrated the synthetic utility of the process as exemplified by their elegant synthesis of nicotine.¨
(a) Wolff M. E. Chem. Rev. 1963, 63, 55. (b) Löffler, K.; Freytag, C. Chem. Ber. 1909, 42, 3427. 4
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Mechanistic Studies
In 1950s and 60s…
Indication that C−H bond cleavage : rate-limiting step of the reaction
(a) Wolff M. E. Chem. Rev. 1963, 63, 55. (b) Wawzonek, S.; Thelan, P. J. J. Am. Chem. Soc. 1950, 72, 2118.(c) Corey, E. J.; Hertler, W. R. J. Am. Chem. Soc. 1960, 78, 1657. 5
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Mechanism
-Initiation :
-Propagation :
-Termination :
-Acidic Conditions :
-Basic Conditions :
6Wolff M. E. Chem. Rev. 1963, 63, 55.
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Rise of Nitrene Chemistry
(a) Breslow, D. S.; Sloan, M. F. Tetrahedron Lett. 1968, 9, 5349.(b) Breslow, D. S.; Edwards, E. I.; Linsay, E. C.; Omura, H. J. Am. Chem. Soc. 1976, 98, 4268. 7
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Rise of C-H Insertion/ and C-H Activation/Amination
C-H Insertion C-H Activation
8(a) Collet, F.; Dodd, R. H.; Dauban, P. Chem. Commun. 2009, 5061. (b) Collet, F.; Lescot, C.; Dauban, P. Chem. Soc. Rev. 2011, 40, 1926.
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Selectfluor Mediated Oxidation of Alcohols and Aldehydes
9Banks, R. E.; Lawrence, N. J.; Popplewell, A. L. Synlett, 1994, 831.
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Unexpected Selectfluor Mediated C-H Functionalization
10Banks, R. E.; Lawrence, N. J.; Besheesh, M. K.; Popplewell, A. L.; Pritchard, R. G. Chem. Commun. 1996, 1629.
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Unexpected Selectfluor Mediated C-H Functionalization
10Banks, R. E.; Lawrence, N. J.; Besheesh, M. K.; Popplewell, A. L.; Pritchard, R. G. Chem. Commun. 1996, 1629.
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Selectfluor Mediated C-H Functionalization
11Banks, R. E.; Lawrence, N. J.; Besheesh, M. K.; Popplewell, A. L.; Pritchard, R. G. Chem. Commun. 1996, 1629.
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Proposed Mechanism - Ritter-Type C−H Amination
12Banks, R. E.; Lawrence, N. J.; Besheesh, M. K.; Popplewell, A. L.; Pritchard, R. G. Chem. Commun. 1996, 1629.
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Ritter Reaction
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Baran…
14Michaudel, Q.; Thevenet, D.; Baran, P. S. J. Am. Chem. Soc. 2012, 134, 2547.
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Optimization
15Michaudel, Q.; Thevenet, D.; Baran, P. S. J. Am. Chem. Soc. 2012, 134, 2547.
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Optimization
15Michaudel, Q.; Thevenet, D.; Baran, P. S. J. Am. Chem. Soc. 2012, 134, 2547.
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C-H Amination with Inexpensive Source of Nitrogen
16Michaudel, Q.; Thevenet, D.; Baran, P. S. J. Am. Chem. Soc. 2012, 134, 2547.
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C-H Amination with Inexpensive Source of Nitrogen
17Michaudel, Q.; Thevenet, D.; Baran, P. S. J. Am. Chem. Soc. 2012, 134, 2547.
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Isomerization of cis-Decalin
18Michaudel, Q.; Thevenet, D.; Baran, P. S. J. Am. Chem. Soc. 2012, 134, 2547.
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Hydrolysis
Michaudel, Q.; Thevenet, D.; Baran, P. S. J. Am. Chem. Soc. 2012, 134, 2547. 19
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Mechanistic Studies
20Michaudel, Q.; Thevenet, D.; Baran, P. S. J. Am. Chem. Soc. 2012, 134, 2547.
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Mechanistic Hypothesis - SET
21(a) Michaudel, Q.; Thevenet, D.; Baran, P. S. J. Am. Chem. Soc. 2012, 134, 2547. (b) Kochi, J. K. Science 1967, 155, 415.
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F+ Mediated Oxidation of Metal; PdII / PdIV – AuI / AuIII
22
(a) Nyffeler, P. T.; Duro ́n, S. G.; Burkart, M. D.; Vincent, S. P.; Wong, C.-H. Angew. Chem., Int. Ed. 2005, 44, 192 . (b) Mei, T.-S.; Wang, X.; Yu, J.-Q. J. Am. Chem. Soc. 2009, 131, 10806. (c) Hull, K. L.; Anani, W. Q.; Sanford, M. S. J. Am. Chem. Soc. 2006, 128, 7134. (d) Rosewall, C. F.; Sibbald, P. A.; Liskin, D. V.; Michael, F. E. J. Am. Chem. Soc. 2009, 131, 9488. (e) Zhang, G.; Cui, L.; Wang, Y.; Zhang, L. J. Am. Chem. Soc. 2010, 132, 1474.