Synthesis and conjugate addition reactions of N-(β-nitroalkyl)amides. Issue 48 (2nd December 2015)

• Record Type: Journal Article
• Authors: Wade, Peter A.; Paparoidamis, Nicholas; Liao, Jennie; Manor, Brian C.; DeBolt, Kristine
• Is Part Of: Tetrahedron letters. Volume 56:Issue 48(2015)
• Page Start: 6722
• Page End: 6725
• Publication Date: 2015-12-02
• Subjects: RHNLFIAHWDALCY-UHFFFAOYSA-N -- YOHFUBSJSUGLBP-UHFFFAOYSA-N -- FVXWPGGXHKUIQP-IUCAKERBSA-N -- FVXWPGGXHKUIQP-BDAKNGLRSA-N -- JGKYHTPZZHZZBC-UHFFFAOYSA-N -- OYDWWBGGMKUUNB-UHFFFAOYSA-N -- RWMJLYZTBZDDEC-UHFFFAOYSA-N -- GKXBKDMKYFXSLW-BRPSZJMVSA-N -- MGHYBWBNIPNKAG-UHFFFAOYSA-N -- BHDOQIFZKPLIFZ-UHFFFAOYSA-N -- GLEXPSUHPLQRRF-UHFFFAOYSA-N -- MXIBMBGZJFTZPQ-QWHCGFSZSA-N -- SZQPJLPGBLRVGY-NWDGAFQWSA-N -- OSJBTJRUSSTUIA-QWHCGFSZSA-N -- KQQZVJQKKPFDGU-IUCAKERBSA-N -- LNIUCCBGWIATKB-UHFFFAOYSA-N; Nitro compound -- Internal H-bonding -- Diastereoselective Michael addition -- Ritter reaction -- Alkene nitration; Chemistry, Organic -- Periodicals; 547.005
• DOI: 10.1016/j.tetlet.2015.10.055
• Languages: English
• ISSNs: 0040-4039

Abstract

Graphical abstract: Abstract: Nitration of several di- and trisubstituted alkenes with lithium nitrate/TFAA in nitrile solvents afforded N -(β-nitroalkyl)amides in 28–72% yields. Nitration of 1, 1-diphenylethene gave 1, 1-diphenyl-2-nitroethene in 52% yield instead of the N -(β-nitroalkyl)amide. Reaction of 1-methylcyclohexene using excess lithium nitrate/TFAA in acetonitrile gave a single diastereomer of N -(2, 6-dinitro-1-cyclohexyl)acetamide in 55% yield. N -(β-Nitroalkyl)amides underwent diastereoselective Michael addition to a variety of Michael acceptors. Diastereoselectivity is rationalized on the basis of internal hydrogen-bonding within the intermediate nitronate resulting in a strongly-biased Michael donor conformation.