Skip to main page content
Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2019 Oct 28;24(21):3883.
doi: 10.3390/molecules24213883.

Carbohydrate-Based Chiral Iodoarene Catalysts: A Survey Through the Development of an Improved Catalyst Design

Affiliations
Free PMC article

Carbohydrate-Based Chiral Iodoarene Catalysts: A Survey Through the Development of an Improved Catalyst Design

Michael R Imrich et al. Molecules. .
Free PMC article

Abstract

Iodoarene catalysts can be applied in versatile reactions, for instance in the construction of complex chiral molecules via dearomatization of simple aromatic compounds. Recently, we reported the synthesis of the first carbohydrate-based chiral iodoarene catalysts and their application in asymmetric catalysis. Here we describe the synthesis of some new and improved catalysts. An account on how we got to the improved catalyst design, as well as the X-ray structure of one of the carbohydrate-based iodoarenes, is given.

Keywords: Mitsunobu reaction; asymmetric catalysis; benzylic substitution; bulky substituent; carbohydrate; dearomatization; iodoarene; organocatalysis; spirolactonization.

Conflict of interest statement

The authors declare no conflicts of interest.

Figures

Scheme 1
Scheme 1
Enantioselective dearomatization of naphthole derivative 1 to 2 catalyzed by a chiral iodoarene.
Figure 1
Figure 1
Some examples of chiral iodoarene catalysts described in the literature [15,16,17,18,19,20].
Scheme 2
Scheme 2
Preparation of catalysts 11, 12, 14, and 15.
Scheme 3
Scheme 3
Synthesis of C1 symmetrical catalysts 17 and 20.
Scheme 4
Scheme 4
Synthesis of carbohydrate derivatives of different monosaccharides with similar substitution patterns at positions 1, 2, 3, and 4 and a hydroxyl group at position 6.
Scheme 5
Scheme 5
Mitsunobu reaction between 2-iodoresorcinol 33 and carbohydrate derivatives 30, 31, and 32 to synthesize catalysts 34, 35, and 36.
Figure 2
Figure 2
Molecular structure of 8c. Ellipsoids are given at the 50% probability level; hydrogens are omitted for better clarity. Grey: carbon, red: oxygen, purple: iodine.
Scheme 6
Scheme 6
Preparation of α-d-glucose-based iodoarenes 44, 45, and 46 with a bulky substituent at position 4 and small methyl groups at positions 1, 2, and 3.
Scheme 7
Scheme 7
Synthesis of 1-naphthylmethyl-substituted catalyst 50.

Similar articles

See all similar articles

References

    1. Lindhorst T.K. Essentials of Carbohydrate Chemistry and Biochemistry. Volume 3 Wiley-VCH; Weinheim, Germany: 2007.
    1. Imrich M.R., Kraft J., Maichle-Mössmer C., Ziegler T. d-Fructose-based spiro-fused PHOX ligands: Synthesis and application in enatioselective allylic alkylation. Beilstein J. Org. Chem. 2018;14:2082–2089. doi: 10.3762/bjoc.14.182. - DOI - PMC - PubMed
    1. Imrich M.R., Maichle-Mössmer C., Ziegler T. d-Fructose based spiro-fused PHOX ligands: Palladium complexes and application in catalysis. Eur. J. Org. Chem. 2019:3955–3963. doi: 10.1002/ejoc.201900490. - DOI - PMC - PubMed
    1. Kraft J., Golkowski M., Ziegler T. Spiro-fused carbohydrate oxazoline ligands: Synthesis and application as enantio-discrimination agents in asymmetric allylic alkylation. Beilstein J. Org. Chem. 2016;12:166. doi: 10.3762/bjoc.12.18. - DOI - PMC - PubMed
    1. Kraft J., Mill K., Ziegler T. Sugar-Annulated Oxazoline Ligands: A Novel Pd (II) Complex and Its Application in Allylic Substitution. Molecules. 2016;21:1704 doi: 10.3390/molecules21121704. - DOI - PMC - PubMed
Feedback