Copper(II)-Catalyzed β-Borylation of Acetylenic Esters in Water

Cheryl L. Peck; Joseph A. Calderone; Webster L. Santos

doi:10.1055/s-0034-1380524

Synthesis, Table of Contents

Synthesis 2015; 47(15): 2242-2248
DOI: 10.1055/s-0034-1380524

special topic

Copper(II)-Catalyzed β-Borylation of Acetylenic Esters in Water

Cheryl L. Peck

Department of Chemistry, Virginia Tech, Blacksburg, VA 24061, USA Email: santosw@vt.edu

,

Joseph A. Calderone

Department of Chemistry, Virginia Tech, Blacksburg, VA 24061, USA Email: santosw@vt.edu

,

Webster L. Santos*

Department of Chemistry, Virginia Tech, Blacksburg, VA 24061, USA Email: santosw@vt.edu

› Author Affiliations

Abstract

All articles of this category

Abstract

A method for the β-borylation of alkynoates has been developed. In the presence of bis(pinacolato)diboron and catalytic amounts of both copper(II) and 4-picoline, substituted alkynoates undergo borylation in a regio-, stereo-, and chemoselective fashion. The reaction is performed under mild conditions using water as solvent and open to the atmosphere to exclusively afford (Z)-β-boryl-α,β-unsaturated esters.

Key words

boron - copper - stereoselectivity - hydroboration - alkynes

Full Text

References

References

1a Hall D. Boronic Acids: Preparation, Applications in Organic Synthesis, Medicine and Materials. Wiley-VCH; Weinheim: 2011. 2nd ed.
1b Takaya J, Iwasawa N. ACS Catal. 2012; 2: 1993
1c Beletskaya I, Moberg C. Chem. Rev. 2006; 106: 2320
1d Burks HE, Morken JP. Chem. Commun. 2007; 4717
1e Brown JM, Nguyen BN. Stereoselective Synthesis 1: Stereoselective Reactions of Carbon—Carbon Double Bonds In Science of Synthesis. Vol. 1. de Vries JG. Thieme; Stuttgart: 2011: 295

2a Thomas RL, Souza FE. S, Marder TB. J. Chem. Soc., Dalton Trans. 2001; 1650
2b Anderson KM, Lesley MJ. G, Norman NC, Orpen AG, Starbuck J. New J. Chem. 1999; 23: 1053
2c Ishiyama T, Matsuda N, Murata M, Ozawa F, Suzuki A, Miyaura N. Organometallics 1996; 15: 713

3 Ishiyama T, Takagi J, Kamon A, Miyaura N. J. Organomet. Chem. 2003; 687: 284
4 Lee J.-E, Kwon J, Yun J. Chem. Commun. 2008; 733

5a Semba K, Fujihara T, Terao J, Tsuji Y. Chem. Eur. J. 2012; 18: 4179
5b Tai C.-C, Yu M.-S, Chen Y.-L, Chuang W.-H, Lin T.-H, Yap GP. A, Ong T.-G. Chem. Commun. 2014; 50: 4344

6a Lipshutz BH, Moser R, Voigtritter KR. Isr. J. Chem. 2010; 50: 691
6b Isley NA, Gallou F, Lipshutz BH. J. Am. Chem. Soc. 2013; 135: 17707

For examples of borylation of α,β-unsaturated carbonyl compounds, see:

7a Chea H, Sim HS, Yun J. Bull. Korean Chem. Soc. 2010; 31: 551
7b Kobayashi S, Xu P, Endo T, Ueno M, Kitanosono T. Angew. Chem. Int. Ed. 2012; 51: 12763
7c Kitanosono T, Kobayashi S. Asian J. Org. Chem. 2013; 2: 961
7d Kitanosono T, Xu P, Kobayashi S. Chem. Commun. 2013; 49: 8184
7e Stavber G, Časar Z. Appl. Organomet. Chem. 2013; 27: 159
7f For a review of copper-catalyzed borylation in water, see: Stavber G, Časar Z. ChemCatChem 2014; 6: 2162

8 Thorpe SB, Calderone JA, Santos WL. Org. Lett. 2012; 14: 1918
9 For reviews, see ref. 1b and: Oestreich M, Hartmann E, Mewald M. Chem. Rev. 2013; 113: 402
10 Cho SH, Hwang SJ, Chang S. J. Am. Chem. Soc. 2008; 130: 9254
11 Barbe G, Pelletier G, Charette AB. Org. Lett. 2009; 11: 3398

Supplementary Material

Supporting Information