Ketene chemistry and the application in synthesisgbdong.cm.utexas.edu/seminar/old/Ketene...
Transcript of Ketene chemistry and the application in synthesisgbdong.cm.utexas.edu/seminar/old/Ketene...
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Ketene chemistry and the
application in synthesis
Dong group at UT Austin
Xuan Zhou
Nov 14, 2013
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Ketene chemistry
Content
• A brief history of ketene
• Type of ketenes
• Ketene preparation
• Ketenes in synthesis
Reviews about ketenes:T. T. Tidwell, Ketenes, 2nd ed., wiley interscience, Hoboken, NJ, 2006.
T. T. Tidwell, Eur. J. Org. Chem. 2006, 563-576.
T. T. Tidwell, Angew. Chem. Int. Ed. 2005, 44, 5778-5785.
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A brief history of ketene
The first reported ketene: Diphenylketene
Wedekind
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Ketene and its Dimer:
N.T.M. Wilsmore, J. Chem. Soc. 1907, 91, 1938
Asymmetric reactions of ketene:
H. Pracejus, Justus liebigs Ann. Chem. 1969, 722, 1-11
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Bisketenes
First prepared bisketenes by Wolf in 1906
O. Diels, B. Wolf, Ber. Dtsch. Chem. Ges. 1906, 39, 689-697
First observed bisketenes in 1982
G. Maier, H. P. Reisenauer, T. Sayrac, Chem. Ber. 1982, 115, 2192
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Substituent effects of ketene
Melvin Newman Shchukovskaya
Cycloadditions of ketenes
Lee Irvin Smith Derek H.R. Barton
Angew. Chem. Int. Ed. 2005, 44, 5779-5785
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Type of ketenes
• Alkylketenes
Carbon-substituted ketenes
2 3 4
•Alkenylketenes
5 6 7
• alkynylketenes and cyanoketenes
8 9 10
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•Arylketenes
1 2 3
•Acylketenes
4 5 6
• Imidoylketenes
azetinones7 8
Type of ketenes
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Nitrogen-substituted ketenes
1 Nitroketene Azidoketene Isocyanatoketene 2
Oxygen-substituted ketenes
3 4 5 6
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Halogen-substituted ketenes
Silyl-ketenes
1 2 3 4
5 6 7
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Phosphorous, sulfur, metal-substituted and bis ketenes
1 2
5 6 7 8
9 10
11 12
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Ketene preparation
Ketenes from ketene dimers
•Pyrolysis of ketene dimer
1 2 3 4
5 6
•Photolysis of ketene dimer
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Ketene from carboxylic anhydrides
1 2 3 4
5
11 12 13
9 10
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Ketenes from acyl halides and activated acids
1 2
3 4 5
6 7
8 9
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Ketenes by dehalogenation of a-Halo carboxylic acid
derivatives
The first prepared ketene
3 4 5
The most common used ketene-dichloroketene
6
9 10
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Ketenes from diazo ketones (Wolff rearrangements)
hv or heat
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Wolff rearrangements in synthesis
51 52 53
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Catalyzed Wolff rearrangements
12
3 4 5
6 7 8
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Ketene from cyclobutanone and cyclobutenone
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Ketene from cyclobutanone and cyclobutenone
88
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Ketenes from dioxinones
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Ketene by thermolysis of Alkynyl ethers
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Cycloaddition reaction of ketenes
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[2+2] cycloaddition of ketenes
Regio-selectivity of [2+2]
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[2+2] cycloaddition of ketenes
Cycloaddition ketenes with Alkenes
Cycloaddition ketenes with nucleophilic alkenes
Cycloaddition ketenes with Allenes
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[2+2] cycloaddition of ketenes
Cycloaddition ketenes with alkynes
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Reactions of ketenes
Cycloaddition ketenes with imines form β-lactam
[3+2] Cycloaddition of ketenes
[4+2] Cycloaddition of ketenes
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Reactions of ketenesIntramolecular cycloaddition of ketenes
cycloaddition of ketenes with carbony groups
27
Nucleophilic addition to ketenes
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Ketenes in synthesis
Ketenes in polymer chemistry
38
C.J. Hawker etc, Nature chem. 2010, 2, 207-212
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Ketenes in polymer chemistry
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Ketenes in synthesis
Total synthesis of macrocidin A
K. Suzuki, Angew. Chem. 2010, 122, 893
69
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Ketenes in synthesis
Total synthesis of (-)-callipeltoside A
H. Zhao, J. Org. Chem. 2010, 75, 7052
67
68
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Ketenes in synthesis
Synthesis antitumer agent (+)-FR900482
1 2
3 4
R. L. Danheiser, J. Org. Chem. 2011, 76, 1852
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Ketenes in synthesis
Bis (β-lactam) preparation
101 102
M. R. Torres, Chem. Eur. J. 2010, 16, 1592
103
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Ketenes in synthesis
K. C. Nicolaou. Angew. Chem. Int. Ed. 1999, 38, 1669
Synthesis CP-263
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Conclusion
Ketene chemistry after 100 years: ready for a new century!
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Thanks!
Congratulations to Huang and Zhe!
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Question 1
Question 2
Question 3