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181

Danheiser annulation
Trimethylsilylcyclopentene annulation from an DE-unsaturated ketone and
trimethylsilylallene in the presence of a Lewis acid.
O

O
SiMe3 TiCl4, CH2Cl2

SiMe3

75 C, 82%

Cl
Cl3Ti

Cl3Ti

Cl

O
SiMe3

SiMe3

Cl3Ti

1,2-shift of
SiMe3

silyl group

Transition State
Cl
Cl3Ti

O
O
SiMe3
SiMe3

182

Example 17

O
TiCl4, CH2Cl2

SiMe3

OMe

78 oC

O
O

OMe
O

OMe
OH

OMe
O

Me3Si

15%

6%

48%

Example 28
O
SiMe3

TiCl4, CH2Cl2

75 oC, 91%

(1:1)
Me3Si

Me3Si

References
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Danheiser, R. L.; Carini, D. J.; Basak, A. J. Am. Chem. Soc. 1981, 103, 1604. Rick L.
Danheiser earned his Ph.D. at Harvard under E. J. Corey. He is a professor at MIT.
Danheiser, R. L.; Carini, D. J.; Fink, D. M.; Basak, A. Tetrahedron 1983, 39, 935.
Danheiser, R. L.; Kwasigroch, C. A.; Tsai, Y.-M. J. Am. Chem. Soc. 1985, 107, 7233.
Danheiser, R. L.; Carini, D. J.; Kwasigroch, C. A. J. Org. Chem. 1986, 51, 3870.
Danheiser, R. L.; Tsai, Y.-M.; Fink, D. M. Org. Synth. 1988, 66, 1.
Danheiser, R. L.; Dixon, B. R.; Gleason, R. W. J. Org. Chem. 1992, 57, 6094.
Engler, T. A.; Agrios, K.; Reddy, J. P.; Iyengar, R. Tetrahedron Lett. 1996, 37, 327.
Friese, J. C.; Krause, S.; Schfer, H. J. Tetrahedron Lett. 2002, 43, 2683.