Silicon Grignard Reagents as Nucleophiles in Transition-Metal-Catalyzed Allylic Substitution

Weichao Xue; Martin Oestreich

doi:10.1055/s-0037-1610309

Synthesis, Inhaltsverzeichnis

CC BY ND NC 4.0 · Synthesis 2019; 51(01): 233-239
DOI: 10.1055/s-0037-1610309

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Silicon Grignard Reagents as Nucleophiles in Transition-Metal-Catalyzed Allylic Substitution

Weichao Xue

,

Martin Oestreich*

Institut für Chemie, Technische Universität Berlin, Strasse des 17. Juni 115, 10623 Berlin, Germany eMail: martin.oestreich@tu-berlin.de

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Abstract

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Published as part of the 50 Years SYNTHESIS – Golden Anniversary Issue

Abstract

A broad range of transition-metal catalysts is shown to promote allylic substitution reactions of allylic electrophiles with silicon Grignard reagents. The procedure was further elaborated for CuI as catalyst. The regioselectively is independent of the leaving group for primary allylic precursors, favoring α over γ. The stereochemical course of this allylic transposition was probed with a cyclic system, and anti-diastereoselectivity was obtained.

Key words

allylic substitution - copper - Grignard reagents - silicon

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Referenzen

References

For recent reviews, see:

1a Denmark SE. Ambrosi A. Org. Process Res. Dev. 2015; 19: 982
1b Yus M. González-Gόmez JC. Foubelo F. Chem. Rev. 2013; 113: 5595
1c Chabaud L. James P. Landais Y. Eur. J. Org. Chem. 2004; 15: 3173

For selected examples with Si–Si compounds, see:

2a Hayashi T. Ohno A. Lu S.-j. Matsumoto Y. Fukuyo E. Yanagi K. J. Am. Chem. Soc. 1994; 116: 4221
2b Moser R. Nishikata T. Lipshutz BH. Org. Lett. 2010; 12: 28
2c Selander N. Paasch JR. Szabό KJ. J. Am. Chem. Soc. 2011; 133: 409
2d Larsson JM. Szabό KJ. J. Am. Chem. Soc. 2013; 135: 443

For selected examples with Si–B compounds, see:

3a Vyas DJ. Oestreich M. Angew. Chem. Int. Ed. 2010; 49: 8513
3b Delvos LB. Vyas DJ. Oestreich M. Angew. Chem. Int. Ed. 2013; 52: 4650
3c Takeda M. Shintani R. Hayashi T. J. Org. Chem. 2013; 78: 5007
3d Hazra CK. Irran E. Oestreich M. Eur. J. Org. Chem. 2013; 4903
3e Delvos LB. Hensel A. Oestreich M. Synthesis 2014; 46: 2957
3f Delvos LB. Oestreich M. Synthesis 2015; 47: 924

For selected examples with silicon zinc reagents, see:

4a Oestreich M. Auer G. Adv. Synth. Catal. 2005; 347: 637
4b Schmidtmann ES. Oestreich M. Chem. Commun. 2006; 3643
4c Vyas DJ. Oestreich M. Chem. Commun. 2010; 46: 568
4d Hensel A. Oestreich M. Chem. Eur. J. 2015; 21: 9062

For nucleophilic substitution of silicon electrophiles with allylic metal reagents, see:

5a Lennon PJ. Mack DP. Thompson QE. Organometallics 1989; 8: 1121
5b Murakami K. Yorimitsu H. Oshima K. J. Org. Chem. 2009; 74: 1415

Other methods hinge on the silylation of 1,3-dienes or allenes or, more recently, involve formal C–H bond silylation:

6a Suginome M. Ohmura T. Miyake Y. Mitani S. Ito Y. Murakami M. J. Am. Chem. Soc. 2003; 125: 11174
6b Larsson JM. Zhao TS. Szabό KJ. Org. Lett. 2011; 13: 1888
6c Miller ZD. Li W. Belderrain TR. Montgomery J. J. Am. Chem. Soc. 2013; 135: 15282
6d MeAtee JR. Yap GP. A. Watson DA. J. Am. Chem. Soc. 2014; 136: 10166
6e Nakai S. Matsui M. Shimizu Y. Adachi Y. Obora Y. J. Org. Chem. 2015; 80: 7317

7 Xue W. Shishido R. Oestreich M. Angew. Chem. Int. Ed. 2018; 57: 12141
8 George MV. Peterson DJ. Gilman H. J. Am. Chem. Soc. 1960; 82: 403
9 Fleming I. Higgins D. Lawrence NJ. Thomas AP. J. Chem. Soc., Perkin Trans. 1 1992; 3331
10 For the preparation of syn-16a, see: Watson ID. G. Yudin AK. J. Am. Chem. Soc. 2005; 127: 17516
11 Fleming I. Thomas AP. J. Chem. Soc., Chem. Commun. 1986; 1456
12 Tamao K. Kawachi A. Ito K. J. Am. Chem. Soc. 1992; 82: 3989

For recent reviews on the synthesis of silicon-stereogenic silanes, see:

13a Xu L.-W. Angew. Chem. Int. Ed. 2012; 51: 12932
13b Cui Y.-M. Lin Y. Xu L.-W. Coord. Chem. Rev. 2017; 330: 37
13c Shintani R. Synlett 2018; 29: 388

14 Yasui K. Fugami K. Tanaka S. Tamaru Y. J. Org. Chem. 1995; 60: 1365
15 Harris RK. Becker ED. Cabral de Menezes R. Goodfellow SM. Granger P. Pure Appl. Chem. 2001; 73: 1795
16 Kofron WG. Baclawski LM. J. Org. Chem. 1976; 41: 1879
17 Krasovskiy A. Knochel P. Synthesis 2006; 890
18 Fleming I. Rowley M. Cuadrado P. González-Nogal AM. Pulido FJ. Tetrahedron 1989; 45: 413
19 Li Z. Yang C. Zheng H. Qiu H. Lai G. J. Organomet. Chem. 2008; 693: 3771
20 Barbero A. Cuadrado P. Gonzalez AM. Pulido FJ. Fleming I. J. Chem. Soc., Perkin Trans. 1 1991; 2811
21 Jorapur YR. Shimada T. Synlett 2012; 23: 1633

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