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. 2018 May 17;24(28):7123-7127.
doi: 10.1002/chem.201801304. Epub 2018 Apr 25.

Enantioselective Catalyst Systems from Copper(II) Triflate and BINOL-Silanediol

Yong Guan  1 , Jonathan W Attard  1 , Michael D Visco  2 , Thomas J Fisher  3 , Anita E Mattson  1
Affiliations

Enantioselective Catalyst Systems from Copper(II) Triflate and BINOL-Silanediol

Yong Guan et al. Chemistry. .

Abstract

Silanediol and copper catalysis are merged, for the first time, to create an enhanced Lewis acid catalyst system for enantioselective heterocycle functionalization. The promise of this silanediol and copper catalyst combination is demonstrated in the enantioselective addition of indoles to alkylidene malonates to give rise to the desirable adducts in excellent yield and high enantiomeric excess. From these studies, 1,1'-bi-2-naphthol (BINOL)-based silanediols emerge as one-of-a-kind cocatalysts. Their potential role in the reaction pathway is also discussed.

Keywords: Friedel-Crafts reactions; cooperative catalysis; copper; enantioselectivity; silanediols.

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Conflict of interest statement

Conflict of interest

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
Expanding the role of silanediols in catalysis: A) substrate activation and B) catalyst activation.
Scheme 1
Scheme 1
Scale-up and recrystallization for the preparation of 4a.
Scheme 2
Scheme 2
Unique combination of silanediol and Cu(OTf)2.
Scheme 3
Scheme 3
Probing of the plausible role of silanediol.
Scheme 4
Scheme 4
Possible catalytic pathway.
See this image and copyright information in PMC

References

    1. For reviews of silanediols, see: Wieting JM, Hardman-Baldwin AM, Visco MD, Mattson AE. Aldrichimica Acta. 2016;49:15–20.Franz AK, Wilson SO. J Med Chem. 2013;56:388.Sieburth SM, Chen CA. Eur J Org Chem. 2006:311.Min GK, Hernandez D, Skrydstrup T. Acc Chem Res. 2013;46:457.

    1. For examples of the medicinal applications of silanediols, see: Sieburth SM, Nittoli T, Mutahi A, Guo L. Angew Chem Int Ed. 1998;37:812.Angew Chem. 1998;110:845.Mutahi MW, Nittoli T, Guo L, Sieburth SM. J Am Chem Soc. 2002;124:7363.

    1. For an application of silanediol molecular recognition in sensing, see: Kondo S, Bie Y, Yamamura M. Org Lett. 2013;15:520–523.

    1. For selected examples of silanediols in achiral catalysis, see: Tran NT, Min T, Franz AK. Chem Eur J. 2011;17:9897.Schafer AG, Wieting JM, Mattson AE. Org Lett. 2011;13:5228–5232.Hardman-Baldwin AM, Mattson AE. ChemSusChem. 2014;7:3275–3278.

    1. For an early report of silanediols in anion recognition, see: Kondo S, Harada T, Tanaka R, Unno M. Org Lett. 2006;8:4621–4624.

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