ANIPE-Cu Catalyst Enables Highly Enantioselective Markovnikov Hydroboration of α-Olefins

Abstract

Asymmetric hydroboration of simple and unactivated terminal alkenes (α-olefins), feedstock chemicals derived from the petrochemical industry, has not been efficiently realized for past decades. Using a bulky ANIPE ligand, we achieved a rare example of highly enantioselective copper-catalyzed Markovnikov hydroboration of α-olefins. The chiral secondary alkylboronic ester products were obtained in moderate to good yields and regioselectivities with excellent enantioselectivities.

1 Introduction

2 Conditions Optimization

3 Substrate Scope

4 Application

5 Mechanistic Discussion

6 Conclusions and Future Directions

Key words

asymmetric hydroboration - α-olefin - copper catalysis - ­ligand design - privileged chiral fragment - N-heterocyclic carbine

Publication History

Received: 26 September 2020

Accepted after revision: 12 October 2020

Accepted Manuscript online:
12 October 2020

Article published online:
27 November 2020

• References

• 1a Chen J, Guo J, Lu Z. Chin. J. Chem. 2018; 36: 1075
• 1b Obligacion JV, Chirik PJ. Nat. Rev. Chem. 2018; 2: 15
• 1c Fan W, Li L, Zhang GJ. J. Org. Chem. 2019; 84: 5987
• 2 Boronic Acids: Preparation and Applications in Organic Synthesis Medicine and Materials. Hall DG. Wiley-VCH; Weinheim: 2011

For reviews on asymmetric hydroboration, see:
• 3a Crudden CM, Edwards D. Eur. J. Org. Chem. 2003; 4695
• 3b Carroll A.-M, O’Sullivan TP, Guiry PJ. Adv. Synth. Catal. 2005; 347: 609
• 3c Thomas SP, Aggarwal VK. Angew. Chem. Int. Ed. 2009; 48: 1896

For selected examples of asymmetric hydroboration, see for Rh:
• 4a Hayashi T, Matsumoto Y, Ito Y. J. Am. Chem. Soc. 1989; 111: 3426
• 4b Crudden CM, Hleba YB, Chen AC. J. Am. Chem. Soc. 2004; 126: 9200
• 4c Hu N, Zhao G, Zhang Y, Liu X, Li G, Tang W. J. Am. Chem. Soc. 2015; 137: 6746
• 4d Chakrabarty S, Takacs JM. J. Am. Chem. Soc. 2017; 139: 6066

For Cu:
• 4e Noh D, Chea H, Ju J, Yun J. Angew. Chem. Int. Ed. 2009; 48: 6062
• 4f Jang WJ, Song SM, Moon JH, Lee JY, Yun J. J. Am. Chem. Soc. 2017; 139: 13660
• 4g Corberan R, Mszar NW, Hoveyda AH. Angew. Chem. Int. Ed. 2011; 50: 7079

For Co:
• 4h Zhang L, Zuo Z, Wan X, Huang Z. J. Am. Chem. Soc. 2014; 136: 15501
• 4i Chen X, Cheng Z, Lu Z. ACS Catal. 2019; 9: 4025
• 4j Yu S, Wu C, Ge S. J. Am. Chem. Soc. 2017; 139: 6526
• 4k Chen X, Cheng Z, Guo J, Lu Z. Nat. Commun. 2018; 9: 3939

For examples of Cu-catalyzed asymmetric formal hydroboration using B₂Pin₂ and alcohol, see:
• 5a Lee Y, Hoveyda AH. J. Am. Chem. Soc. 2009; 131: 3160
• 5b Corberan R, Mszar NW, Hoveyda AH. Angew. Chem. Int. Ed. 2011; 50: 7079
• 5c Sasaki Y, Zhong C, Sawamura M, Ito H. J. Am. Chem. Soc. 2010; 132: 1226
• 5d Parra A, Amenos L, Guisan-Ceinos M, Lopez A, García Ruano JL, Tortosa M. J. Am. Chem. Soc. 2014; 136: 15833
• 5e Chen L, Shen J.-J, Gao Q, Xu S. Chem. Sci. 2018; 9: 5855

For selected examples of Cu-catalyzed asymmetric 1,4- or 1,6-borylation, see:
• 6a Chen I.-H, Yin L, Itano W, Kanai M, Shibasaki M. J. Am. Chem. Soc. 2009; 131: 11664
• 6b Lee J.-E, Yun J. Angew. Chem. Int. Ed. 2008; 47: 145
• 6c Luo Y, Roy ID, Madec AG. E, Lam HW. Angew. Chem. Int. Ed. 2014; 53: 4186
• 6d Lou Y, Cao P, Jia T, Zhang Y, Wang M, Liao J. Angew. Chem. Int. Ed. 2015; 54: 12134
• 7 Xi Y, Hartwig JF. J. Am. Chem. Soc. 2016; 138: 6703
• 8a Coombs JR, Morken JP. Angew. Chem. Int. Ed. 2016; 55: 2636
• 8b Chen J, Lu Z. Org. Chem. Front. 2018; 5: 260
• 9a Cherian AE, Lobkovsky EB, Coates GW. Chem. Commun. 2003; 2566
• 9b Cherian AE, Domski GJ, Rose JM, Lobkovsky EB, Coates GW. Org. Lett. 2005; 7: 5135
• 10a Wang F, Liu L.-J, Wang W, Li S, Shi M. Coord. Chem. Rev. 2012; 256: 804
• 10b Janssen-Müller D, Schlepphorst C, Glorius F. Chem. Soc. Rev. 2017; 46: 4845
• 11a Albright A, Gawley RE. J. Am. Chem. Soc. 2011; 133: 19680
• 11b Albright A, Eddings D, Black R, Welch CJ, Gerasimchuk NN, Gawley RE. J. Org. Chem. 2011; 76: 7341
• 11c Spahn E, Albright A, Shevlin M, Pauli L, Pfaltz A, Gawley RE. J. Org. Chem. 2013; 78: 2731
• 12 Cai Y, Yang X.-T, Zhang S.-Q, Li F, Li Y.-Q, Ruan L.-X, Hong X, Shi S.-L. Angew. Chem. Int. Ed. 2018; 57: 1376

Other works:
• 13a Cai Y, Zhang J.-W, Li F, Liu J.-M, Shi S.-L. ACS Catal. 2019; 9: 1
• 13b Zhang W.-B, Yang X.-T, Ma J.-B, Su Z.-M, Shi S.-L. J. Am. Chem. Soc. 2019; 141: 5628
• 13c Shen D, Xu Y, Shi S.-L. J. Am. Chem. Soc. 2019; 141: 14938
• 13d Cai Y, Ye X, Liu S, Shi S.-L. Angew. Chem. Int. Ed. 2019; 58: 13433
• 13e Shen D, Zhang W.-B, Li Z, Shi S.-L, Xu Y. Adv. Synth. Catal. 2020; 362: 1125

For a concomitant development of ligands, see:
• 13f Diesel J, Finogenova AM, Cramer N. J. Am. Chem. Soc. 2018; 140: 4489
• 14a Wang Z.-C, Shen D, Gao J, Jia X, Xu Y, Shi S.-L. Chem. Commun. 2019; 55: 8848
• 14b Wang Z.-C, Wang M, Gao J, Shi S.-L, Xu Y. Org. Chem. Front. 2019; 6: 2949
• 14c Li F, Bai X, Cai Y, Li H, Zhang S.-Q, Liu F.-H, Hong X, Xu Y, Shi S.-L. Org. Process Res. Dev. 2019; 23: 1703

For relevant reports during our research or after our contributions, see:
• 15a Smith JR, Collins BS. L, Hesse MJ, Graham MA, Myers EL, Aggarwal VK. J. Am. Chem. Soc. 2017; 139: 9148
• 15b Iwamoto H, Imamoto T, Ito H. Nat. Commun. 2018; 9: 2290
• 16a Sadhu KM, Matteson DS. Organometallics 1985; 4: 1687
• 16b Sonawane RP, Jheengut V, Rabalakos C, Larouche-Gauthier R, Scott HK, Aggarwal VK. Angew. Chem. Int. Ed. 2011; 50: 3760
• 16c Llaveria J, Leonori D, Aggarwal VK. J. Am. Chem. Soc. 2015; 137: 10958
• 17a Poater A, Cosenza B, Correa A, Giudice S, Ragone F, Scarano V, Cavallo L. Eur. J. Inorg. Chem. 2009; 13: 1759
• 17b Falivene L, Cao Z, Petta A, Serra L, Poater A, Oliva R, Scarano V, Cavallo L. Nat. Chem. 2019; 11: 827