Hosomi-Sakurai Reaction

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.

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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.

Recent Literature

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. Lett., 2003, 5, 55-57.

o-Benzenedisulfonimide as a Reusable Brønsted Acid Catalyst for Hosomi-Sakurai Reactions
M. Barbero, S. Bazzi, S. Cadamuro, S. Dughera, C. Piccinini, Synthesis, 2010, 315-319.

Efficient Brønsted Acid Catalyzed Hosomi-Sakurai Reaction of Acetals
D. Kampen, B. List, Synlett, 2006, 2589-2592.

Microwave-Assisted Allylation of Acetals with Allyltrimethylsilane in the Presence of CuBr
M. E. Jung, A. Maderna, J. Org. Chem., 2004, 69, 7755-7757.

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, 7, 3219-3222.

A General Catalytic Allylation Using Allyltrimethoxysilane
S. Yamasaki, K. Fujii, R. Wada, M. Kanai, M. Shibasaki, J. Am. Chem. Soc., 2002, 124, 6536-6537.

FeSO₄·7H₂O-Catalyzed Four-Component Synthesis of Protected Homoallylic Amines
Q.-Y. Song, B.-L. Yang, S.-K. Tian, J. Org. Chem., 2007, 72, 5407-5410.

Interruption of Formal Schmidt Rearrangement/Hosomi-Sakurai Reaction of Vinyl Azides with Allyl/Propargylsilanes
G. Fang, Z. Liu, S. Cao, H. Yuan, J. Zhang, L. Pan, Org. Lett., 2018, 20, 7113-7116.

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, 2003, 2390-2394.

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, 71, 8516-8522.

Generation of Cations from Alkoxides: Allylation of Propargyl Alcohols
G. W. Kabalka, M.-L. Yao, S. Borella, J. Am. Chem. Soc., 2006, 128, 11320-11321.

Efficient Addition of Allylsilanes to α,β-Enones Using Catalytic Indium and Trimethylsilyl Chloride
P. H. Lee, D. Seomoon, S. Kim, K. Nagaiah, S. V. Damle, K. Lee, Synthesis, 2003, 2023-2026.

A Highly Stereospecific Claisen-Sakurai Approach to Densely Functionalized Cyclopentenols
K. S. Stankevich, M. J. Cook, J. Org. Chem., 2022, 87, 12250-12256.

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.