Sakurai allylation reaction
Lewis酸催化下烯丙基硅烷作为碳亲核试剂进行烯丙基化的反应。此反应也被称为 Hosomi–Sakurai反应。底物如果是单纯的羰基化合物，则产物为醇。
反应机理
β-硅效应可以稳定β为的碳正离子。
反应实例
参考文献
1. Hosomi, A.; Sakurai, H. Tetrahedron Lett. 1976, 1295–1298. Hideki Sakurai was a professor at Tohuko University in Japan. This reaction is also known as the Hosomi–Sakurai reaction.
2. Majetich, G.; Behnke, M.; Hull, K. J. Org. Chem. 1985, 50, 3615–3618.
3. Tori, M.; Makino, C.; Hisazumi, K.; Sono, M.; Nakashima, K. Tetrahedron: Asymmetry 2001, 12, 301–307.
4. Leroy, B.; Markó, I. E. J. Org. Chem. 2002, 67, 8744–8752.
5. Itsuno, S.; Kumagai, T. Helv. Chim. Acta 2002, 85, 3185–3196.
6. Trost, B. M.; Thiel, O. R.; Tsui, H.-C. J. Am. Chem. Soc. 2003, 125, 13155–13164.
7. Knepper, K.; Ziegert, R. E.; Bräse, S. Tetrahedron 2004, 60, 8591–8603.
8. Rikimaru, K.; Mori, K.; Kan, T.; Fukuyama, T. Chem. Commun. 2005, 394–396.
9. Jervis, P. J.; Kariuki, B. M.; Cox, L. R. Org. Lett. 2006, 8, 4649–4652.
10. Kalidindi, S.; Jeong, W. B.; Schall, A.; Bandichhor, R.; Nosse, B.; Reiser, O. Angew. Chem. Int. Ed. 2007, 46, 6361–6363.
11. Norcross, N. R.; Melbardis, J. P.; Solera, M. F.; Sephton, M. A.; Kilner, C.; Zakharov, L. N.; Astles, P. C.; Warriner, S. L.; Blakemore, P. R. J. Org. Chem. 2008, 73, 7939–7951.
12. Li, L.; Ye, X.; Wu, Y.; Gao, L.; Song, Z.; Yin, Z.; Xu, Y. Org. Lett. 2013, 15, 1068–1071.
编译自：Name Reactions （A Collection of Detailed Reaction Mechanisms）, Jie Jack Li, Sakurai allylation reaction，page 527-528.
之前有关此反应的介绍
概要
烯丙基硅参与的烯丙基化反应。烯丙基硅试剂是相对烯丙基锡毒性低、比烯丙基格利雅试剂及锂试剂稳定的有机合成试剂。
常加入Lewis酸，氟化物来推动反应进行。特别是，在lewis酸作用下，烯丙基格氏试剂，烯丙基锂试剂按γ位選択进行、根据底物不同能达到很好的立体选择性。还有共轭烯醇的烯丙基化反应只按照共轭加成的方式进行。
基本文献
・Hosomi, A.; Endo, M.; Sakurai, H. Chem. Lett. 1976, 941. doi:10.1246/cl.1976.941
・Hosomi, A.; Sakurai, H. Tetrahedron Lett. 1976, 17, 1295. doi:10.1016/S0040-4039(00)78044-0
・Hosomi, A.; Sakurai, H. J. Am. Chem. Soc. 1977, 99, 1673. DOI: 10.1021/ja00447a080
・Wilson, S. R.; Price, M.F. J. Am. Chem. Soc. 1982, 104, 1124. DOI: 10.1021/ja00368a049
・Review: Fleming, I. et al. Org. React. 1989, 37, 57.
・Review: Fleming, I. Comprehensive Organic Syntheis 1991, 2, 563.
反应机理
烯丙基β位的碳正离子是因超共轭的原因，较稳定。在此基础上提出以下的反应机理。硅的lewis酸性较弱，反应按非环状过渡态进行。(Tetrahedron Lett. 1983, 24, 2865.)
反应实例
Denmark等人、开发的用手性lewis碱实现了不对称烯丙基化。[1]
山本等人、用氟化银基手性不对称膦配体，将反应活性差，选择性低的酮实现对映选择性的烯丙基化。[2]
Furaquinocin A的合成[3]
Halichlorine的合成[4]
环状氧鎓盐的细见-樱井反应以高立体选择性进行。6元环的4位取代基及五元环的3位取代基对烯丙基化的作用较大。[5]
实验步骤
不饱和酮的共轭烯丙基化[6]
实验技巧
参考文献
[1] Denmark, S. E.; Coe, D. M.; Pratt, N. E.; Griedel, B. E. J. Org. Chem. 1994, 59, 6161. DOI:10.1021/jo00100a013
[2] Wadamoto, M.; Yamamoto, H. J. Am. Chem. Soc. 2005, 127, 14556. DOI: 10.1021/ja0553351
[3] Trost, B. M.; Thiel, O. R.; Tsui, H.-C. J. Am. Chem. Soc. 2003, 125, 13155. DOI: 10.1021/ja0364118
[4] (a) Trauner, D.; Schwartz, J. B.; Danishefsky, S. J. Angew. Chem. Int. Ed. 1999, 38, 3542.[abstract] (b) Trauner, D.; Danishefsky, S. J. Tetahedron Lett. 1999, 40, 6513. doi:10.1016/S0040-4039(99)01170-3
[5] (a) Woerpel, K. A. et al. J. Am. Chem. Soc. 1999, 121. 12208. DOI: 10.1021/ja993349z (b) Woerpel, K. A. et al. J. Am. Chem. Soc. 2003, 125, 14149. DOI: 10.1021/ja0375176 (c) Woerpel, K. A. et al. J. Am. Chem. Soc. 2003, 125, 15521. DOI: 10.1021/ja037935a (d) Woerpel, K. A. et al. J. Am. Chem. Soc. 2005, 127, 10879. DOI: 10.1021/ja0524043
[6] Org. Synth. 1984, 62, 84.
转自“化学空间”
Hosomi Sakurai反应是指在路易斯酸催化下各种亲电试剂和烯丙基三甲基硅烷反应进行烯丙基化的反应。此反应中Lewis酸是反应能够进行的关键。
反应机理
Note: 硅烷对β 碳正离子有稳定作用 (β effect)
在一些反应中只需要催化量的Lewis酸就能进行反应，但反应中要使用烯丙基氯硅烷而不是烯丙基三甲基硅烷：
A. Fürstner, D. Voigtländer, Synthesis, 2000, 959-969.
最新文献
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.
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.
编译自：organic chemistry portal