Tf2O/TTBP (2,4,6-Tri- tert-butylpyrimidine): An Alternative Amide Activation System for the Direct Transformations of Both Tertiary and Secondary Amides

Qian He; Jian-Liang Ye; Fang-Fang Xu; Hui Geng; Ting-Ting Chen; Hang Chen; Pei-Qiang Huang

doi:10.1021/acs.joc.1c01572

Tf₂O/TTBP (2,4,6-Tri- tert-butylpyrimidine): An Alternative Amide Activation System for the Direct Transformations of Both Tertiary and Secondary Amides

J Org Chem. 2021 Dec 3;86(23):16300-16314. doi: 10.1021/acs.joc.1c01572. Epub 2021 Sep 9.

Authors

Qian He¹, Jian-Liang Ye¹, Fang-Fang Xu¹, Hui Geng¹, Ting-Ting Chen¹, Hang Chen¹, Pei-Qiang Huang¹

Affiliation

¹ Department of Chemistry and Fujian Provincial Key Laboratory of Chemical Biology, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005, P. R. China.

PMID: 34499513
DOI: 10.1021/acs.joc.1c01572

Abstract

Ten types of Tf₂O/TTBP-mediated amide transformation reactions were investigated. The results showed that compared with pyridine derivatives 2,6-di-tert-butyl-4-methylpyridine (DTBMP) and 2-fluoropyridine (2-F-Pyr.), TTBP can serve as an alternative amide activation system for the direct transformation of both secondary and tertiary amides. For most surveyed examples, higher or comparable yields were generally obtained. In addition, Tf₂O/TTBP combination was used to promote the condensation reactions of 2-(tert-butyldimethylsilyloxy)furan (TBSOF) with both tertiary and secondary amides, the one-pot reductive Bischler-Napieralski-type reaction of tertiary lactams, and Movassaghi and Hill's modern version of the Bischler-Napieralski reaction. The value of the Tf₂O/TTBP-based methodology was further demonstrated by the concise and high-yielding syntheses of several natural products.

Publication types

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

MeSH terms

Amides*
Lactams*
Molecular Structure

Substances

Amides
Lactams