摘要：KEYWORDS:skeletalediting (反应类型),nitrogen deletion (反应类型), amines (原料), DPPH (试剂), C(sp3)–C(sp3) (成键类型);
转自：康龙化成
C(sp3)–C(sp3) Bond Formation Through Nitrogen Deletion of Secondary Amines Using O-diphenylphosphinylhydroxylamine
TingGuo, Jinghao Li, Zhangkai Cui, Zefan Wang & Hongjian Lu
School of Chemistry and ChemicalEngineering, Nanjing University, China
—Nat.Synth. 2024, 3,913–921.
Recommended by Bing Han_MC3
KEYWORDS: skeletalediting (反应类型),nitrogen deletion (反应类型), amines (原料), DPPH (试剂), C(sp3)–C(sp3) (成键类型);
ABSTRACT: Thenitrogen deletion of secondary amines has emerged as an effective strategy fordirect molecular skeletal editing and carbon–carbon bond formation. However,current methods are often limited to acyclic bis(α-primary) amines and cyclicamines, which possess two stabilizing elements at the α-position of amine. Herewe report the use of O-diphenylphosphinylhydroxylamine as areagent for nitrogen deletion of secondary amines to form C(sp3)–C(sp3)bonds. This method overcomes substrate requirements of other methods andtolerates a range of secondary amine substrates. The process can be readilyapplied to multiple nitrogen deletion processes, is tolerant of both air andwater, forms water-soluble byproducts and can be readily scaled to ahundred-gram scale. The versatility of the method is further showcased throughthe direct editing of natural products, pharmaceutical compounds, N-coordinatedligands, a three-dimensional amine cage and the synthesis of several bioactivecompounds.
Background
Optimizationof Reaction Conditions
Selected SubstrateScope
1)Scope of acyclic amines
2) Scope of cyclic amines
Deaminoalkylation of bioactive primary amines
N-deletionof bioactive secondary amines
Prof.Lu and his co-workers reported an innovative N-deletion method-aone-step synthetic procedure utilizing the commercially available reagent DPPH with water as asolvent or cosolvent, and a straight-forward experimental setup. Theversatility of this method is evident in its ability to constructvarious C(sp3)–C(sp3) bonds in the α-position of(hetero) arenes, encompassing 1℃–1℃, 1℃–2℃, 2℃–2℃, 1℃ -3℃ and 2℃–3℃ bonds through the consumption of readily available C(sp3)–Nbonds.
来源：新浪财经
