Tags

Type your tag names separated by a space and hit enter

Toward a synthetically useful stereoselective C-H amination of hydrocarbons.
J Am Chem Soc. 2008 Jan 09; 130(1):343-50.JA

Abstract

Reaction between a sulfur(VI) compound and an iodine(III) oxidant in the presence of a catalytic quantity (<=3 mol %) of a rhodium(II) catalyst leads to the formation of a chiral metallanitrene of unprecedented reactivity. The latter allows intermolecular C-H amination to proceed in very high yields up to 92% and excellent diastereoselectivities up to 99% with C-H bond containing starting materials as the limiting component. The scope of this C-H functionalization includes benzylic and allylic substrates as well as alkanes. Secondary positions react preferentially, but insertion into activated primary C-H bonds or sterically accessible tertiary sites is also possible. Cooperative effects between the nitrene precursor and the chiral catalyst at the origin of these good results have also been applied to kinetic resolution of racemic sulfonimidamide. This methodology paves the way to the use of Csp3-H bonds as synthetic precursors for the introduction of a nitrogen functionality into selected positions.

Authors+Show Affiliations

Institut de Chimie des Substances Naturelles, UPR 2301, CNRS, Avenue de la Terrasse, F-91198 Gif-sur-Yvette, France.No affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info available

Pub Type(s)

Journal Article
Research Support, Non-U.S. Gov't

Language

eng

PubMed ID

18072775

Citation

Liang, Chungen, et al. "Toward a Synthetically Useful Stereoselective C-H Amination of Hydrocarbons." Journal of the American Chemical Society, vol. 130, no. 1, 2008, pp. 343-50.
Liang C, Collet F, Robert-Peillard F, et al. Toward a synthetically useful stereoselective C-H amination of hydrocarbons. J Am Chem Soc. 2008;130(1):343-50.
Liang, C., Collet, F., Robert-Peillard, F., Müller, P., Dodd, R. H., & Dauban, P. (2008). Toward a synthetically useful stereoselective C-H amination of hydrocarbons. Journal of the American Chemical Society, 130(1), 343-50.
Liang C, et al. Toward a Synthetically Useful Stereoselective C-H Amination of Hydrocarbons. J Am Chem Soc. 2008 Jan 9;130(1):343-50. PubMed PMID: 18072775.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Toward a synthetically useful stereoselective C-H amination of hydrocarbons. AU - Liang,Chungen, AU - Collet,Florence, AU - Robert-Peillard,Fabien, AU - Müller,Paul, AU - Dodd,Robert H, AU - Dauban,Philippe, Y1 - 2007/12/12/ PY - 2007/12/13/pubmed PY - 2008/1/26/medline PY - 2007/12/13/entrez SP - 343 EP - 50 JF - Journal of the American Chemical Society JO - J Am Chem Soc VL - 130 IS - 1 N2 - Reaction between a sulfur(VI) compound and an iodine(III) oxidant in the presence of a catalytic quantity (<=3 mol %) of a rhodium(II) catalyst leads to the formation of a chiral metallanitrene of unprecedented reactivity. The latter allows intermolecular C-H amination to proceed in very high yields up to 92% and excellent diastereoselectivities up to 99% with C-H bond containing starting materials as the limiting component. The scope of this C-H functionalization includes benzylic and allylic substrates as well as alkanes. Secondary positions react preferentially, but insertion into activated primary C-H bonds or sterically accessible tertiary sites is also possible. Cooperative effects between the nitrene precursor and the chiral catalyst at the origin of these good results have also been applied to kinetic resolution of racemic sulfonimidamide. This methodology paves the way to the use of Csp3-H bonds as synthetic precursors for the introduction of a nitrogen functionality into selected positions. SN - 1520-5126 UR - https://www.unboundmedicine.com/medline/citation/18072775/Toward_a_synthetically_useful_stereoselective_C_H_amination_of_hydrocarbons_ L2 - https://doi.org/10.1021/ja076519d DB - PRIME DP - Unbound Medicine ER -