250261-56-4Relevant academic research and scientific papers
The aza-wharton reaction: Syntheses of cyclic allylic amines and vicinal hydroxyamines from the respective acylaziridines
Silva, Saúl,Rodrigues, Paula,Bento, Isabel,Maycock, Christopher D.
, p. 3067 - 3074 (2015/03/30)
The Wharton reaction, initially described for acyl epoxides, has been studied using the structurally similar aziridines. By this reaction, a range of cyclic allylic amines and vicinal amino alcohols have been prepared stereoselectively and, in some cases, enantiomerically pure.
Semipinacol rearrangement of cis-fused β-lactam diols into keto-bridged bicyclic lactams
Grainger, Richard S.,Betou, Marie,Male, Louise,Pitak, Mateusz B.,Coles, Simon J.
supporting information; experimental part, p. 2234 - 2237 (2012/06/30)
The 6-azabicyclo[3.2.1]octane ring system, prevalent in a range of biologically active molecules, is prepared through a novel semipinacol rearrangement utilizing a cyclic phosphorane or sulfite intermediate. The rearrangement proceeds with exclusive N-acyl group migration of a β-lactam ring and results in carbonyl functionality at the 7- and bridging 8-position of the bicycle. Precursor ring-fused β-lactam diols are prepared through a sequence of 4-exo trig carbamoyl radical cyclization, regioselective dithiocarbamate group elimination, and dihydroxylation.
cis- and trans-Stereoselective Epoxidation of N-Protected 2-Cyclohexen-1-ylamines
O'Brien, Peter,Childs, Amanda C.,Ensor, Gareth J.,Hill, Cheryl L.,Kirby, Jonathan P.,Dearden, Michael J.,Oxenford, Sally J.,Rosser, Clare M.
, p. 4955 - 4957 (2007/10/03)
(Equation Presented) The first systematic study of the cis and trans stereoselectivity in the m-CPBA epoxidation of N-protected cyclic allylic amines has been completed. Mono-N-protected systems gave epoxides with cis stereochemistry (amides are better ci
A general nickel-catalyzed hydroamination of 1,3-dienes by alkylamines: Catalyst selection, scope, and mechanism
Pawlas, Jan,Nakao, Yoshiaki,Kawatsura, Motoi,Hartwig, John F.
, p. 3669 - 3679 (2007/10/03)
A simple colorimetric assay of various transition-metal catalysts showed that the combination of DPPF, Ni(COD)2, and acid is a highly active catalyst system for the hydroamination of dienes by alkylamines to form allylic amines. The scope of the reaction is broad; various primary and secondary alkylamines react with 1,3-dienes in the presence of these catalysts. Detailed mechanistic studies revealed the individual steps involved in the catalytic process. These studies uncovered unexpected thermodynamics for the addition of amines to π-allyl nickel complexes: instead of the thermodynamics favoring the reaction of a nickel allyl with an amine to form an allylic amine, the thermodynamics favored reaction of a nickel(0) complex with allylic amine in the presence of acid to form a Ni(II) allyl. The realization of these thermodynamics led us to the discovery that nickel and some palladium complexes in the presence or absence of acid catalyze the exchange of the amino groups of allylic amines with free amines. This exchange process was used to reveal the relative thermodynamic stabilities of various allylic amines. In addition, this exchange reaction leads to racemization of allylic amines. Therefore, the relative rate for C-N bond formation and cleavage influences the enantioselectivity of diene hydroaminations.
Stereoselective synthesis of (3R*,3aS*,7aS*)-3-aryloctahydroindol2-ones using radical cyclisation: A formal synthesis of (±)-pancracine
Ikeda, Masazumi,Hamada, Masahiro,Yamashita, Takashi,Matsui, Katsuaki,Sato, Tatsunori,Ishibashi, Hiroyuki
, p. 1949 - 1956 (2007/10/03)
The Bu3SnH- or (TMS)3SiH-mediated 5-emlo-trig radical cyclisation of the 7V-(cyclohex-l-enyl)acetamide 10 gives a mixture of the as-fused (3R*,3aS*,7aS*)- and trans-fused (3R*,3aS*,7aK*)-3-aryloctahydroindol-2-ones lia and lib, whereas the 5-cxo-trig radical cyclisation of the N-(cycIohex-2-enyl)acetamide 17 proceeds in a stereoselective manner to give only lia. The latter method has been applied to the synthesis of the 5,11-methanomorphanthridine derivative 30, a key intermediate for the synthesis of (±)-pancracine 1.
