Subscribe to RSS
Please copy the URL and add it into your RSS Feed Reader.
https://www.thieme-connect.de/rss/thieme/en/10.1055-s-00000083.xml
Synlett 2014; 25(2): 239-242
DOI: 10.1055/s-0033-1340282
DOI: 10.1055/s-0033-1340282
letter
Synthesis of Tertiary Allylboronates from Vinylboronates
Further Information
Publication History
Received: 02 September 2013
Accepted after revision: 14 October 2013
Publication Date:
04 December 2013 (online)
![](https://www.thieme-connect.de/media/synlett/201402/lookinside/thumbnails/10.1055-s-0033-1340282-1.jpg)
Abstract
Allylic boronates are versatile intermediates in organic synthesis. Herein, we present an ‘ate-mediated allylic substitution’ (AMAS) approach to allylic boronates. Bifunctional vinylboroate/ allylic acetate esters react with Grignard reagents to form tertiary allylic boronates via an AMAS reaction. We demonstrate that the method tolerates a wide range of substrates and Grignard reagents.
Supporting Information
- for this article is available online at http://www.thieme-connect.com/ejournals/toc/synlett.
- Supporting Information
-
References and Notes
- 1a Contemporary Boron Chemistry . Davidson M, Hughes AK, Marder TB, Wade K. RSC; Cambridge: 2000
- 1b Boronic Acids . Hall DG. Wiley-VCH; Weinhein: 2005
- 1c Crudden CM. Chem. Commun. 2009; 45: 6704
- 1d Jiao J, Nishihara Y. J. Organomet. Chem. 2012; 721-722: 3
-
1e Cid J, Gulyas H, Carbo JJ, Fernandez E. Chem. Soc. Rev. 2012; 41: 3558
- 2a Hall DG. Pure Appl. Chem. 2008; 80: 913
- 2b Carosi L, Hall DG. Can. J. Chem. 2009; 87: 650
- 2c Guiry PJ. ChemCatChem 2009; 1: 233
- 2d Mkhalid IA. I, Barnard JH, Marder TB, Murphy JM, Hartwig JF. Chem. Rev. 2010; 110: 890
-
2e Wu H, Radomkit S, O’Brien J, Hoveyda A. J. Am. Chem. Soc. 2012; 134: 8277
- 3a Hoffmann RW, Landmann B. Chem. Ber. 1986; 119: 2013
- 3b Sato M, Yamamoto Y, Hara S, Suzuki A. Tetrahedron Lett. 1993; 34: 7071
- 3c Schlapbach A, Hoffmann RW. Eur. J. Org. Chem. 2001; 323
- 3d Lombardo M, Morganti S, Tozzi M, Trombini C. Eur. J. Org. Chem. 2002; 2823
- 3e Pietruszka J, Schöne N. Angew. Chem. Int. Ed. 2003; 42: 5638
- 3f Han J.-L, Chen M, Roush WR. Org. Lett. 2013; 14: 3028
- 3g Nuhant P, Roush WR. J. Am. Chem. Soc. 2013; 135: 5340
- 3h Chen M, Roush WR. J. Am. Chem. Soc. 2013; 135: 9512
- 3i Yang Y, Buchwald SL. J. Am. Chem. Soc. 2013; 135: 10642
- 4a Matteson DS. J. Organomet. Chem. 1999; 581: 51
- 4b Aggarwal VK, Fang GY, Ginesta X, Howells DM, Zaja M. Pure Appl. Chem. 2006; 78: 215
- 4c Thomas SP, French RM, Jheengut V, Aggarwal VK. Chem. Rec. 2009; 9: 24
- 5a Matteson DS, Liedtke JD. J. Org. Chem. 1963; 28: 1924
- 5b Tufariello JJ, Lee LT. C, Wojtkowski P. J. Am. Chem. Soc. 1967; 89: 6804
- 5c Matteson DS, Majumdar D. J. Am. Chem. Soc. 1980; 102: 7588
- 5d Matteson DS, Hurst GD. Organometallics 1986; 5: 1465
- 5e Brown HC, Singh SM, Rangaishenvi MV. J. Org. Chem. 1986; 51: 3150
- 5f Aggarwal VK, Harvey JN, Robiette R. Angew. Chem. Int. Ed. 2005; 44: 5468
- 6a Matteson DS, Ray R. J. Am. Chem. Soc. 1980; 102: 7590
- 6b Matteson DS, Ray R, Rocks RR, Tsai DJ. Organometallics 1983; 2: 1536
- 6c Matteson DS, Sadhu KM, Peterson ML. J. Am. Chem. Soc. 1986; 108: 810
- 6d Matteson DS. Acc. Chem. Res. 1988; 21: 294
- 6e Matteson DS. Chem. Rev. 1989; 89: 1535
- 6f Matteson DS, Michnick TJ. Organometallics 1990; 9: 3171
- 6g Matteson DS, Man H.-W. J. Org. Chem. 1994; 59: 5734
- 6h Aggarwal VK, Fang GY, Schmidt AT. J. Am. Chem. Soc. 2005; 127: 1642
- 6i Fang GY, Wallner OA, Blasio ND, Ginesta X, Harvey JN, Aggarwal VK. J. Am. Chem. Soc. 2007; 129: 14632
- 6j Dutheuil G, Webster MP, Worthington PA, Aggarwal VK. Angew. Chem. Int. Ed. 2009; 48: 6317
- 6k Schmidt F, Keller F, Vedrenne E, Aggarwal VK. Angew. Chem. Int. Ed. 2009; 48: 1149
- 6l Vedrenne E, Wallner OA, Vitale M, Schmidt F, Aggarwal VK. Org. Lett. 2009; 11: 165
- 7a Matteson DS, Majumdar D. Organometallics 1983; 2: 1529
- 7b Sadhu KM, Matteson DS. Organometallics 1985; 4: 1687
- 7c Brown HC, Rangaishenvi MV, Jayaraman S. Organometallics 1992; 11: 1948
- 8a Stymiest JL, Bagutski V, French RM, Aggarwal VK. Nature 2008; 456: 778
- 8b Bagutski V, French RM, Aggarwal VK. Angew. Chem. Int. Ed. 2010; 49: 5142
- 8c Shimizu M. Angew. Chem. Int. Ed. 2011; 50: 5998
- 8d Scott HK, Aggarwal VK. Chem. Eur. J. 2011; 17: 13124
- 8e Sonawane RP, Jheengut V, Rabalakos C, Larouche-Gauthier R, Scott HK, Aggarwal VK. Angew. Chem. Int. Ed. 2011; 50: 3760
- 9a Lombardo M, Morganti S, Tozzi M, Trombini C. Eur. J. Org. Chem. 2002; 2823
- 9b Pietruszka J, Schӧne N. Angew. Chem. Int. Ed. 2003; 42: 5638
- 9c Berrée F, Gernigon N, Hercouet A, Lin CH, Carboni B. Eur. J. Org. Chem. 2009; 329
- 9d Vogt M, Ceylan S, Kirschning A. Tetrahedron 2010; 66: 6450
- 10a Hoffmann RW, Dresely S. Angew. Chem., Int. Ed. Engl. 1986; 25: 189
- 10b Schlapbach A, Hoffmann RW. Eur. J. Org. Chem. 2001; 323
- 10c Carosi L, Hall DG. Angew. Chem. Int. Ed. 2007; 46: 5913
- 10d Carosi L, Hall DG. Can. J. Chem. 2009; 87: 650
- 11a Takahashi K, Ishiyama T, Miyaura N. J. Organomet. Chem. 2001; 625: 47
- 11b Ito H, Sasaki Y, Sawamura M. J. Am. Chem. Soc. 2008; 130: 15774
- 11c Lee J.-E, Kwon J, Yun J. Chem. Commun. 2008; 44: 733
- 11d Lipshutz BH, Bošković ŽV, Aue DH. Angew. Chem. Int. Ed. 2008; 47: 10183
-
11e Lee Y, Jang H, Hoveyda AH. J. Am. Chem. Soc. 2009; 131: 18234
-
11f Kim HR, Jung IG, Yoo K, Jang K, Lee ES, Yun J, Son SU. Chem. Commun. 2010; 46: 758
-
11g Jang H, Zhugralin AR, Lee Y, Hoveyda AH. J. Am. Chem. Soc. 2011; 133: 7859
- 11h Kim HR, Yun J. Chem. Commun. 2011; 47: 2943
- 11i Sasaki Y, Horita Y, Zhong C, Sawamura M, Ito H. Angew. Chem. Int. Ed. 2011; 50: 2778
- 11j Moure AL, Gómez Arrayás R, Cárdenas DJ, Alonso I, Carretero JC. J. Am. Chem. Soc. 2012; 134: 7219
- 11k Semba K, Fujihara T, Terao J, Tsuji Y. Chem. Eur. J. 2012; 18: 4179
-
12 Park JK, Ondrusek BA, McQuade DT. Org. Lett. 2012; 14: 4790
- 13 Hesse MJ, Butts CP, Willis CL, Aggarwal VK. Angew. Chem. Int. Ed. 2012; 51: 12444
- 14 The results of such an oxidation to yield a tertiary allylic alcohol are included in the Supporting Information. Compounds not found within the text are numbered sequentially beginning with 9.
- 15 A mechanistic rationale for E-selectivity is included in the Supporting Information.
For recent reviews on boron chemistry, see:
For recent general reviews on homologation chemistry, see:
For asymmetric examples, see: