Synthesis 2017; 49(21): 4738-4744
DOI: 10.1055/s-0036-1588802
special topic
© Georg Thieme Verlag Stuttgart · New York

Copper(I)-Catalyzed Boryl Substitution of Allyl Aminals: Selective Synthesis of Linear γ-Aminoallylboronates

Yuta Takenouchi
Division of Applied Chemistry and Frontier Chemistry Center, Faculty of Engineering, Hokkaido University, Sapporo, Hokkaido, 060-8628, Japan   Email: hajito@eng.hokudai.ac.jp
,
Division of Applied Chemistry and Frontier Chemistry Center, Faculty of Engineering, Hokkaido University, Sapporo, Hokkaido, 060-8628, Japan   Email: hajito@eng.hokudai.ac.jp
› Author Affiliations
This study was financially supported by the MEXT (Japan) program (Strategic Molecular and Materials Chemistry through Innovative Coupling Reactions) of Hokkaido University, as well as
Further Information

Publication History

Received: 08 February 2017

Accepted after revision: 30 March 2017

Publication Date:
15 May 2017 (eFirst)

Published as part of the Special Topic Modern Strategies for Borylation in Synthesis

Abstract

A novel approach for the selective synthesis of α-substituted γ-aminoallylboronates through a copper(I)-catalyzed γ-boryl-substitution of allyl aminals is developed. The reaction proceeds with high yield (up to 88%) and good E/Z selectivity (up to >95:5). Subsequent aldehyde allylation using allylboronates affords (Z)-anti-1,2-amino alcohol derivatives with high stereoselectivity (up to 91% yield, and up to 17:83 E/Z).

Supporting Information

 
  • References

    • 1a Lee H.-S. Kang SH. Synlett 2004; 1673
    • 1b Bergmeier SC. Tetrahedron 2000; 56: 2561
    • 1c Karjalainen OK. Koskinen AM. P. Org. Biomol. Chem. 2012; 10: 4311
    • 2a Tao B. Schlingloff G. Sharpless KB. Tetrahedron Lett. 1998; 39: 2507
    • 2b Demko ZP. Bartsch M. Sharpless KB. Org. Lett. 2000; 2: 2221
    • 2c Wang C. Yamamoto H. J. Am. Chem. Soc. 2014; 136: 6888
    • 3a Lombardo M. Mosconi E. Pasi F. Petrini MA. Trombini C. J. Org. Chem. 2007; 72: 1834
    • 3b Keinicke L. Fristrup P. Norrby PA. Madsen R. J. Am. Chem. Soc. 2005; 127: 15756
    • 3c List B. Pojarliev P. Biller WT. Martin HJ. J. Am. Chem. Soc. 2002; 124: 827
    • 3d Matsunaga S. Yoshida T. Morimoto H. Kumagai N. Shibasaki M. J. Am. Chem. Soc. 2004; 126: 8777
    • 3e Enders D. Grondal C. Vrettou M. Raabe G. Angew. Chem. Int. Ed. 2005; 44: 4079
    • 3f Trost BM. Jaratjaroonphong J. Reutrakul V. J. Am. Chem. Soc. 2006; 128: 2778
    • 3g Carswell EL. Snapper ML. Hoveyda AH. Angew. Chem. Int. Ed. 2006; 45: 7230
    • 3h Ramasastry SS. V. Zhang H. Tanaka F. Barbas CF. III. J. Am. Chem. Soc. 2006; 129: 288
    • 3i Zhong Y.-W. Dong Y.-Z. Fang K. Izumi K. Xu M.-H. Lin G.-Q. J. Am. Chem. Soc. 2005; 127: 11956
    • 3j Skucas E. Zbieg JR. Krische MJ. J. Am. Chem. Soc. 2009; 131: 5054
    • 4a Barrett AG. M. Seefeld MA. Tetrahedron 1993; 49: 7857
    • 4b Barrett AG. M. Seefeld MA. J. Chem. Soc., Chem. Commun. 1993; 339
    • 4c Barrett AG. M. Seefeld MA. Williams DJ. J. Chem. Soc., Chem. Commun. 1994; 1053
    • 4d Barrett AG. M. Seefeld MA. White AJ. P. Williams DJ. J. Org. Chem. 1996; 61: 2677
    • 4e Diner C. Szabó KJ. J. Am. Chem. Soc. 2016; 139: 2
    • 5a Lessard S. Peng F. Hall DG. J. Am. Chem. Soc. 2009; 131: 9612
    • 5b Ding J. Hall DG. Angew. Chem. Int. Ed. 2013; 52: 1
    • 6a Yamamoto E. Takenouchi Y. Ozaki T. Miya T. Ito H. J. Am. Chem. Soc. 2014; 136: 16515
    • 6b Takenouchi Y. Kojima R. Momma R. Ito H. Synlett 2017; 28: 270
    • 7a Ito H. Kawakami C. Sawamura M. J. Am. Chem. Soc. 2005; 127: 16034
    • 7b Ito H. Sasaki Y. Sawamura M. J. Am. Chem. Soc. 2008; 130: 15774
    • 7c Ito H. Okura T. Matsuura K. Sawamura M. Angew. Chem. Int. Ed. 2010; 49: 560
    • 7d Guzman-Martinez A. Hoveyda AH. J. Am. Chem. Soc. 2010; 132: 10634
    • 8a Ito H. Kunii S. Sawamura M. Nat. Chem. 2010; 2: 972
    • 8b Park JK. Lackey HH. Ondrusek BA. McQuade DT. J. Am. Chem. Soc. 2011; 133: 2410
    • 8c Park JK. McQuade DT. Angew. Chem. Int. Ed. 2012; 51: 2717
  • 9 Ito H. Toyoda T. Sawamura M. J. Am. Chem. Soc. 2010; 132: 5990
  • 10 Zhong C. Kunii S. Kosaka Y. Sawamura M. Ito H. J. Am. Chem. Soc. 2010; 132: 11440
  • 11 Zhao J. Szabó KJ. Angew. Chem. Int. Ed. 2016; 55: 1502
  • 12 Lee H. Han HT. Yun J. ACS Catal. 2016; 6: 6487
    • 13a Kano T. Yurino T. Asakawa D. Maruoka K. Angew. Chem. Int. Ed. 2013; 125: 5642
    • 13b Kano T. Kobayashi R. Maruoka K. Angew. Chem. Int. Ed. 2015; 54: 1