Stevens, Sommelet-Hauser and Related Rearrangements
Literature Presentation
April 4th, 2011
Presented by
Louis-Philippe Beaulieu
Gatineau (Aylmer), Qc
1842
2011
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Stevens and Sommelet Biographical Sketches
Thomas Stevens Stevens (1900−2000)
was born in Renfrew, Scotland, UK. He
received his Ph.D at Oxon, became
University Assistant at Glasgow in 1925
and Lecturer in 1933. He is also known for
the McFadyen-Stevens synthesis of
aldehydes and the Bamford-Stevens
elimination reaction, which converts
ketones to alkenes.
Marcel Sommelet (1877−1952) was
born in Langes, France. He received his
Ph.D. In 1906 at Paris where he joined the
Faculté de Pharmacie after WWI and
became the chair of organic chemistry in
1934.
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Program
• Biographical Sketches of Stevens and Sommelet
• The Stevens Rearrangement: Seminal Discovery
Mechanistic Studies
• The Sommelet-Hauser Rearrangement: Seminal Discovery
Mechanistic Studies
• Competition Between [1,2] and [2,3] Pathways
• Different Methods for Ylide Generation
• Asymmetric Versions: C to C Chirality Transfer
C to N Chirality Transfer
Strictly Enantioselective Stevens Rearrangement
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The Stevens Rearrangement: Seminal Discovery
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T. S. Stevens, E. M. Creighton, A. B. Gordon, M. MacNicol, J. Chem. Soc., 1928, 3193.
Intramolecular Nature of the Rearrangement
T. S. Stevens, J. Chem. Soc., 1930, 2107.
R. A. W. Johnstone, T. S. Stevens, J. Chem. Soc. 1955, 4487.
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Retention of Stereogenic Information
J. H. Brewster, M. W. Kline, J. Am. Chem. Soc. 1952, 74, 5179.
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Involvement of a Nitrogen Ylide
R. W. Jemison, S. Mageswaran, W. D. Ollis, S. E. Potter, A. J. Pretty, I. O. Sutherland, Y. Thebtaranonth,
J. Chem. Soc., Chem. Commun. 1970, 1201.
T. Thomson, T. S. Stevens, J. Chem. Soc. 1932, 55.
J. L. Dunn, T. S. Stevens, J. Chem. Soc. 1932, 1926.
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Ion Pair Mechanism vs. Concerted Intramolecular Displacement
T. Thomson, T. S. Stevens, J. Chem. Soc. 1932, 55.
J. L. Dunn, T. S. Stevens, J. Chem. Soc. 1932, 1926.
R. Hoffmann, R. B. Woodward, Acc. Chem. Res. 1968, 1, 17.
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Chemically Induced Dynamic Nuclear Polarization (CIDNP) Mechanistic Study
CIDNP : Non-Boltzmann nuclear spin state distribution produced in thermal or
photochemical reactions, usually from colligation and diffusion, or disproportionation
of radical pairs, and detected by NMR spectroscopy by enhanced absorption or emission signals.
IUPAC Compendium of Chemical Terminology
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Chemically Induced Dynamic Nuclear Polarization (CIDNP) Mechanistic Study
CIDNP : Non-Boltzmann nuclear spin state distribution produced in thermal or
photochemical reactions, usually from colligation and diffusion, or disproportionation
of radical pairs, and detected by NMR spectroscopy by enhanced absorption or emission signals.
DNP : results from transferring spin polarization from electrons to nuclei, thereby aligning the
nuclear spins to the extent that electron spins are aligned.
IUPAC Compendium of Chemical Terminology
Pavia, D. L.; Lampman, G. M.; Kriz, G. S. Introduction to Spectroscopy; Vondeling, J., Kiselica, S., Eds.;
Thomson Learning, 2001; p. 108.
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Chemically Induced Dynamic Nuclear Polarization (CIDNP) Mechanistic Study
A. R. Lepley, J. Am. Chem. Soc. 1969, 91, 1237.
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Radical Pair Mechanistic Patway
W. D. Ollis, M. Rey, I. O. Sutherland, J. Chem. Soc., Perkin Trans. 1 1983, 1009.
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Radical Pair Mechanistic Patway
W. D. Ollis, M. Rey, I. O. Sutherland, J. Chem. Soc., Perkin Trans. 1 1983, 1009.
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Sommelet-Hauser Reaction: Seminal Discovery
Sommelet, M. Compt. Rend. 1937, 205, 56.
S. W. Kantor, C. R. Hauser, J. Am. Chem. Soc. 1951, 73, 4122.
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Mechanistic Insight Through Intermediate Isolation/Trapping
C. R. Hauser, D. N. Van Eenam, J. Am. Chem. Soc. 1957, 79, 5512.
S. H. Pine, B. L. Sanchez, Tetrahedron Lett. 1969, 10, 1319.
16
Competition Between [1,2] and [2,3] Pathways
E. Tayama, K. Takedachi, H. Iwamoto, E. Hasegawa, Tetrahedron 2010, 66, 9389.
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Competition Between [1,2] and [2,3] Pathways
E. Tayama, K. Takedachi, H. Iwamoto, E. Hasegawa, Tetrahedron 2010, 66, 9389.
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Competition Between [1,2] and [2,3] Pathways
[1,2] Stevens rearrangement
Favored in nonpolar organic solvents
(ether, hexanes)
and high temperatures
Sommelet-Hauser rearrangement
Favored in polar solvents
(NH3, DMSO, HMPA)
And low temperatures
Formation of intermediate SHI is
significantly less endoergic
(35 kcal mol-1) according to
M05-2x DFT calculations
E. Tayama, K. Takedachi, H. Iwamoto, E. Hasegawa, Tetrahedron 2010, 66, 9389.
G. Ghigo, S. Cagnina, A. Maranzana, G. Tonachini, J. Org. Chem. 2010, 75, 3608.
Kürti, L.; Czakó, B. Strategic Applications of Named Reactions in Organic Synthesis; Hayhurst, J.; Marr, D., Eds.; Elsevier Academic
Press, 2005; p. 422.
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Base-Mediated Formation of Ylides: Some Drawbacks
Dealkylation
F. E. Ray, J. L. Farmer, J. Org. Chem. 1943, 08, 391.
E. Vedejs, D. A. Engler, M. J. Mullins, The Journal of Organic Chemistry 1977, 42, 3109.
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Base-Mediated Formation of Ylides: Some Drawbacks
Hoffmann Elimination
Regioselectivity of Ylide Generation
L. P. A. Fery, L. van Hove, Bull. Soc. Chim. Belg. 1960, 69, 79.
C. L. Bumgardner, H.-B. Hsu, F. Afghahi, W. L. Roberts, S. T. Purrington, J. Org. Chem. 1979, 44, 2348.
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Fluoride-Mediated Fromation of Ylides
E. Vedejs, G. R. Martinez, J. Am. Chem. Soc. 1979, 101, 6452.
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Direct Formation of Ylides from Diazo Compounds Under Metal Catalysis
M. P. Doyle, W. H. Tamblyn, V. Bagheri, J. Org. Chem. 1981, 46, 5094.
J. A. Vanecko, H. Wan, F. G. West, Tetrahedron 2006, 62, 1043.
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Asymmetric Versions: C to C Chirality Transfer
S. Hanessian, M. Mauduit, Angew. Chem., Int. Ed. 2001, 40, 3810.
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Asymmetric Versions: C to C Chirality Transfer
S. Hanessian, M. Mauduit, Angew. Chem., Int. Ed. 2001, 40, 3810.
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Asymmetric Versions: C to C Chirality Transfer
S. Hanessian, M. Mauduit, Angew. Chem., Int. Ed. 2001, 40, 3810.
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Asymmetric Versions: C to C Chirality Transfer
S. Hanessian, M. Mauduit, Angew. Chem., Int. Ed. 2001, 40, 3810.
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Asymmetric Versions: C to C Chirality Transfer
S. Hanessian, C. Talbot, P. Saravanan, Synthesis 2006, 723.
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Asymmetric Versions: C to C Chirality Transfer
S. Hanessian, C. Talbot, P. Saravanan, Synthesis 2006, 723.
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Asymmetric Versions: C to C Chirality Transfer
S. Hanessian, C. Talbot, P. Saravanan, Synthesis 2006, 723.
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Asymmetric Versions: C to C Chirality Transfer
S. Hanessian, C. Talbot, P. Saravanan, Synthesis 2006, 723.
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Asymmetric Versions: N to C Chirality Transfer
K. W. Glaeske, F. G. West, Org. Lett. 1999, 1, 31.
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Asymmetric Versions: N to C Chirality Transfer
K. W. Glaeske, F. G. West, Org. Lett. 1999, 1, 31.
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Asymmetric Versions: N to C Chirality Transfer
E. Tayama, S. Nanbara, T. Nakai, Chem. Lett. 2006, 35, 478.
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Asymmetric Versions: C to C Chirality Transfer
I. G. Stara, I. Stary, M. Tichy, J. Zavada, V. Hanus, J. Am. Chem. Soc. 1994, 116, 5084.
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Asymmetric Versions: C to C Chirality Transfer
I. G. Stara, I. Stary, M. Tichy, J. Zavada, V. Hanus, J. Am. Chem. Soc. 1994, 116, 5084.
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Strictly Enantioselective Stevens Rearrangement
M.-H. GonAalves-Farbos, L. Vial, J. m. Lacour, Chem. Commun. 2008, 829.
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Strictly Enantioselective Stevens Rearrangement
M.-H. GonAalves-Farbos, L. Vial, J. m. Lacour, Chem. Commun. 2008, 829.
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Strictly Enantioselective Stevens Rearrangement
M.-H. GonAalves-Farbos, L. Vial, J. m. Lacour, Chem. Commun. 2008, 829.
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