Catalytic, Enantioselective Nucleophilic Addition to N-Phosphinoylimines Third Walden Symposium Riga, Latvia

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by William Schulz Bechara
Charette/Collins Literature Meeting November
13th, 2012
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The History of CH 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.
3
The History of CH 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.
Hofmann made the surprising discovery that a
tertiary amine was obtained, and this product was
later shown to be octahydroindolizine.
(a) Wolff M. E. Chem. Rev. 1963, 63, 55. (b)
Hofmann, A. W. Chem. Ber. 1879, 12, 984.
4
The History of CH 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.
Hofmann made the surprising discovery that a
tertiary amine was obtained, and this product was
later shown to be octahydroindolizine.
(a) Wolff M. E. Chem. Rev. 1963, 63, 55. (b)
Hofmann, A. W. Chem. Ber. 1879, 12, 984.
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Isolation of Intermediates
Wolff M. E. Chem. Rev. 1963, 63, 55.
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Isolation of Intermediates
Wolff M. E. Chem. Rev. 1963, 63, 55.
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HofmannLöfflerFreytag 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.
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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.
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Mechanism
-Acidic Conditions
-Initiation
-Propagation
-Termination
-Basic Conditions
Wolff 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.
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Rise of C-H Insertion/ and C-H Activation/Aminatio
n
C-H Insertion C-H Activation
(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
Banks, R. E. Lawrence, N. J. Popplewell, A. L.
Synlett, 1994, 831.
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Unexpected Selectfluor Mediated C-H
Functionalization
Banks, 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
Banks, 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
Banks, 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
Banks, 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
Michaudel, Q. Thevenet, D. Baran, P. S. J. Am.
Chem. Soc. 2012, 134, 2547.
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Optimization
Michaudel, Q. Thevenet, D. Baran, P. S. J. Am.
Chem. Soc. 2012, 134, 2547.
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Optimization
Michaudel, 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
Michaudel, 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
Michaudel, Q. Thevenet, D. Baran, P. S. J. Am.
Chem. Soc. 2012, 134, 2547.
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Isomerization of cis-Decalin
Michaudel, 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.
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Mechanistic Studies
Michaudel, Q. Thevenet, D. Baran, P. S. J. Am.
Chem. Soc. 2012, 134, 2547.
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Mechanistic Hypothesis - SET
(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
(a) Nyffeler, P. T. Duron, 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.