2583-71-3Relevant academic research and scientific papers
Copper-Catalyzed Asymmetric Propargylation of Cyclic Aldimines
Fandrick, Daniel R.,Hart, Christine A.,Okafor, Ifeanyi S.,Mercadante, Michael A.,Sanyal, Sanjit,Masters, James T.,Sarvestani, Max,Fandrick, Keith R.,Stockdill, Jennifer L.,Grinberg, Nelu,Gonnella, Nina,Lee, Heewon,Senanayake, Chris H.
, p. 6192 - 6195 (2016)
The copper-catalyzed asymmetric propargylation of cyclic aldimines is reported. The influence of the imine trimer to inhibit the reaction was identified, and equilibrium constants between the monomer and trimer were determined for general classes of imines. Asymmetric propargylation of a diverse series of N-alkyl and N-aryl aldimines was achieved with good to high asymmetric induction. The utility was demonstrated by a titanium catalyzed hydroamination and reduction to generate the chiral indolizidines (-)-crispine A and (-)-harmicine.
Total synthesis of novel skeleton flavan-alkaloids
Simon, James E.,Wu, Qingli,Zhen, Jing
, (2020/10/18)
The first total synthesis of novel skeleton natural compounds kinkeloids A and B, a group of newly discovered flavan alkaloids isolated fromthe African plant Combretum micranthum, are described in this study. The key and final step are achieved by Mannich reaction, through which the piperidine moiety couples to the flavan moiety. The identities of synthesized kinkeloids were further confirmed through a comparison with the ones in the plant leaves extract using LC/MS.
Acetylenes as Potential Antarafacial Components in Concerted Reactions. Formation of Pyrroles from Thermolyses of Propargylamines, of a Dihydrofuran from a Propargylic Ether, and of an Ethylidenepyrrolidine from a β-Amino Acetylene
Viola, Alfred,Collins, John J.,Filipp, Nicholas,Locke, John S.
, p. 5067 - 5075 (2007/10/02)
A thermal cyclization of acetylenic compounds provides evidence for the ability of acetylenic links to act as antarafacial components in processes.The cyclization competes with the normally favored acetylenic retro-ene reaction.Propargylic amines, without substituents whose presence would hinder a tight cyclic transition state, yield intermediate pyrrolines whose subsequent hydrogen elimination affords pyrroles in small amounts.The same process in 2-ethynyltetrahydropyran affords 8-oxabicyclooctane in 35percent yield.A related thermal reaction of N-methyl-3-hexyn-1-amine provides a quantitative transformation to N-methyl-2-ethylidenepyrrolidine in a nominal s + 2a + 2s + 2s> Moebius process, wherein the acetylenic unit is the antarafacial component.Evidence for concertedness in these reactions is discussed.
Electrochemical Generation of Reactive Nitrogen Species. 10. Anodic Amination of Tetrahydrofuran
Fuchigami, Toshio,Sato, Takashi,Nonaka, Tsutomu
, p. 366 - 369 (2007/10/02)
Anodic oxidation in THF of aminyl anions (lithium amides and aminomagnesium bromides) together with free aliphatic amines efficiently afforded 2-aminotetrahydrofurans.A similar reaction took place in the anodic oxidation of N-lithiolactams.These reactions are the first examples of anodic amination of an aliphatic saturated ether.
Ligation and Reduction of Iron(III) Porphyrins by Amines. A Model for Cytochrome P-450 Monoamine Oxidase
Castro, C. E.,Jamin, Mary,Yokoyama, W.,Wade, Ruth
, p. 4179 - 4187 (2007/10/02)
The scope and mechanism of the ligation and reduction of iron(III) porphyrins by amines are presented.The reaction is general and proceeds with the overall stoichiometry 2PFe(III)Cl + 5RNH2 -> 2PFe(II)(H2NR)2 + R'CH=NH + 2RNH3(1+)Cl(1-).Imines are the only amine-derived products.The ability of the amine to coordinate iron and its possession of a >CHNH moiety are essential for reduction.The reaction path antails two successive reversible ligation steps followed by two one-electron reductions of the bis(amine)-ligated low-spin iron(III) adduct.In benzene the kinetics are biphasic.The second ligation is rate limiting 1(ligation > k(reduction) > k2(ligation)>.In dimethylformamide the first reduction step is rate limiting.The influence of nonreducing amines, porphyrin substituent, axial ligands, and deuteration of the substrate upon the kinetics leads to the formulation of the first reduction as a reversible outer-sphere electron transfer to the porphyrin periphery.This is followed by a rapid conversion of the generated aminium cation radical to an α-aminocarbinyl radical.The latter completes the reduction in an irreversible second step.The relevance of this chemistry to related transformation catalyzed by cytochrome P-450 is discussed.
