107733-62-0Relevant articles and documents
Amination of(η3-allyl)dicarbonylnitrosyliron complexes: A route to γ- amino-α,β-unsaturated carboxylic acid derivatives
Nakanishi, Saburo,Okamoto, Kenji,Yamaguchi, Hiroshi,Takata, Toshikazu
, p. 1735 - 1741 (1998)
Amines reacted regioselectively with (ν3-allyl)dicarbonylnitrosyliron complexes having ester group on the allyl ligand to give γ-amino-α,β- unsaturated esters in high yields. A remarkable effect of the substituents attached to the allyl ligand was observed on the reaction rate and regioselectivity of the amination. The methoxycarbonyl group significantly accelerates the reaction rate and enhances the regioselectivity of the reaction. The phenyl group retards the reaction, but enhances the regioselectivity, while alkyl groups retard the reaction and diminish the regioselectivity.
Unexpected Rearrangement of N-Allyl-2-phenyl-4,5-Dihydrooxazole-4-Carboxamides to Construct Aza-Quaternary Carbon Centers
Choi, Goyeong,Jo, Seoyoung,Mun, Juyeon,Jeong, Yonguk,Kim, Seok-Ho,Jung, Jong-Wha
, (2019/12/25)
The unexpected rearrangement of N-allyl-2-phenyl-4,5-dihydrooxazole-4-carboxamides in the presence of LiHMDS has been found. The key features are: (1) the net reaction consisted of 1,3-migration of the N-allyl group, (2) the rearrangement produced a congested aza-quaternary carbon center, (3) both cyclic and acyclic substrates underwent the unexpected rearrangement to afford products in moderate to high yields, and (4) the reaction seemed to be highly stereoselective. In addition, a plausible mechanism has been discussed.
A Simple, Broad-Scope Nickel(0) Precatalyst System for the Direct Amination of Allyl Alcohols
Sweeney, Joseph B.,Ball, Anthony K.,Lawrence, Philippa A.,Sinclair, Mackenzie C.,Smith, Luke J.
supporting information, p. 10202 - 10206 (2018/08/06)
The preparation of allylic amines is traditionally accomplished by reactions of amines with reactive electrophiles, such as allylic halides, sulfonates, or oxyphosphonium species; such methods involve hazardous reagents, generate stoichiometric waste streams, and often suffer from side reactions (such as overalkylation). We report here the first broad-scope nickel-catalysed direct amination of allyl alcohols: An inexpensive NiII/Zn couple enables the allylation of primary, secondary, and electron-deficient amines without the need for glove-box techniques. Under mild conditions, primary and secondary aliphatic amines react smoothly with a range of allyl alcohols, giving secondary and tertiary amines efficiently. This “totally catalytic” method can also be applied to electron-deficient nitrogen nucleophiles; the practicality of the process was demonstrated in an efficient, gram-scale preparation of the calcium antagonist drug substance flunarizine (Sibelium).
