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.

---

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:

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.

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.