The Hosomi Sakurai Reaction involves the Lewis acid-promoted allylation of various
electrophiles with allyltrimethysilane. Activation by Lewis acids is
critical for an efficient allylation to take place.
Mechanism of the Hosomi-Sakurai Reaction
Note: Silicon stabilizes β carbocations (β effect)
Only catalytic amounts of Lewis acid are needed in some newer protocols. Note
the use of allylsilyl chlorides instead of allyltrimethylsilane:
A. Fürstner, D. Voigtländer,
Synthesis, 2000, 959-969.
Silver-Catalyzed Asymmetric Sakurai-Hosomi Allylation of Ketones
M. Wadamoto, H. Yamamoto, J. Am. Chem. Soc., 2005, 127, 14556-14557.
Synthesis of Homoallyl Ethers via Allylation of Acetals in Ionic Liquids
Catalyzed by Trimethylsilyl Trifluoromethanesulfonate
H. M. Zerth, N. M. Leonard, R. S. Mohan, Org.
2003, 5, 55-57.
o-Benzenedisulfonimide as a Reusable Brønsted Acid Catalyst for
M. Barbero, S. Bazzi, S. Cadamuro, S. Dughera, C. Piccinini, Synthesis, 2010,
Efficient Brønsted Acid Catalyzed Hosomi-Sakurai Reaction of Acetals
D. Kampen, B. List, Synlett, 2006,
Microwave-Assisted Allylation of Acetals with Allyltrimethylsilane in the
Presence of CuBr
M. E. Jung, A. Maderna, J. Org. Chem.,
METHOX: A New Pyridine N-Oxide Organocatalyst for the Asymmetric Allylation of Aldehydes with Allyltrichlorosilanes
A. V. Malkov, M. Bell, F. Castelluzzo, P.
Kocovsky, Org. Lett., 2005,
A General Catalytic Allylation Using Allyltrimethoxysilane
S. Yamasaki, K. Fujii, R. Wada, M. Kanai, M. Shibasaki, J. Am. Chem. Soc., 2002,
FeSO4·7H2O-Catalyzed Four-Component Synthesis of Protected Homoallylic
Q.-Y. Song, B.-L. Yang, S.-K. Tian, J. Org. Chem., 2007,
A selective coupling of alkynylsilanes and allyltrimethylsilane is catalyzed
by 5 mol% of indium tribromide under mild conditions to afford the corresponding
α,β-acetylenic ketones and β,γ-unsaturated ketones in excellent yields.
J. S. Yadav, B. V. S. Reddy, M. Sridhar Reddy, G. Parimala, Synthesis,
An enhanced Lewis acid system of InCl3 and Me3SiBr can be used to promote a
wide range of direct coupling reactions between alcohols and silyl nucleophiles
in non-halogenated solvents. Highly chemoselective allylations toward a hydroxyl
moiety over ketone and acetoxy ones have been demonstrated.
T. Saito, Y. Nishimoto, M. Yasuda, A. Baba, J. Org. Chem., 2006,
Generation of Cations from Alkoxides: Allylation of Propargyl Alcohols
G. W. Kabalka, M.-L. Yao, S. Borella, J. Am. Chem. Soc., 2006,
Efficient Addition of Allylsilanes to α,β-Enones Using Catalytic Indium and
P. H. Lee, D. Seomoon, S. Kim, K. Nagaiah, S. V. Damle, K. Lee, Synthesis,
Stereoselective Synthesis of 2,4,5-Trisubstituted Tetrahydropyrans Using an
Intramolecular Allylation Strategy
P. J. Jervis, B. M. Kariuki, L. R. Cox, Org. Lett., 2006, 8, 4637-4640.