Sakurai allylation refers to the allylation reaction of allyltrimethylsilane with various electrophilic reagents catalyzed by Lewis acid. This reaction is also known as the hosomi Sakurai reaction. Lewis acid is the key to the reaction. Allyl silicon reagent is an organic synthetic reagent which has low toxicity and is more stable than allyl Grignard reagent and lithium reagent.
reaction mechanism
Note: silane has a stable effect on β - carbocation (β effect, hyperconjugation effect)
In some reactions, only Lewis acid of catalytic amount is needed, but allylchlorosilane is used instead of allyltrimethylsilane:
A. Fürstner, D. Voigtl?nder, Synthesis, 2000, 959-969.
Reaction example
M. Wadamoto, H. Yamamoto, J. Am. Chem. Soc., 2005, 127, 14556-14557.
H. M. Zerth, N. M. Leonard, R. S. Mohan, Org. Lett., 2003, 5, 55-57.
M. Barbero, S. Bazzi, S. Cadamuro, S. Dughera, C. Piccinini, Synthesis, 2010, 315-319.
D. Kampen, B. List, Synlett, 2006, 2589-2592.
M. E. Jung, A. Maderna, J. Org. Chem., 2004, 69, 7755-7757.
A. V. Malkov, M. Bell, F. Castelluzzo, P. Kocovsky, Org. Lett., 2005, 7, 3219-3222.
S. Yamasaki, K. Fujii, R. Wada, M. Kanai, M. Shibasaki, J. Am. Chem. Soc., 2002, 124, 6536-6537.
Q.-Y. Song, B.-L. Yang, S.-K. Tian, J. Org. Chem., 2007, 72, 5407-5410.
J. S. Yadav, B. V. S. Reddy, M. Sridhar Reddy, G. Parimala, Synthesis, 2003, 2390-2394.
T. Saito, Y. Nishimoto, M. Yasuda, A. Baba, J. Org. Chem., 2006, 71, 8516-8522.
G. W. Kabalka, M.-L. Yao, S. Borella, J. Am. Chem. Soc., 2006, 128, 11320-11321.
P. H. Lee, D. Seomoon, S. Kim, K. Nagaiah, S. V. Damle, K. Lee, Synthesis, 2003, 2023-2026.
P. J. Jervis, B. M. Kariuki, L. R. Cox, Org. Lett., 2006, 8, 4637-4640.
【 J. Org. Chem. 1985, 50, 3615–3618.】
【J. Am. Chem. Soc. 2003, 125, 13155–13164】
【Org. Lett. 2006, 8, 4649–4652】
【Angew. Chem. Int. Ed. 2007, 46, 6361–6363】
【J. Org. Chem. 2008, 73, 7939–7951】
【Org. Lett. 2013, 15, 1068–1071】
Related literature
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.; Br?se, 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.
Reference
1、 Name reactions (a collection of detailed reaction mechanisms), Jie Jack Li, Sakurai alliance reaction, page 527-528
2、 Organic chemistry portal: https://www.organic-chemistry.org/namedreams/hosomi-sakurai-reaction.shtm