Synthesis of a plasmenylethanolamine

A concise synthesis of a plasmenylethanolamine (PlsEtn-[16:0/18:1 n-9]), known as antioxidative phospholipids commonly found in cell membranes, has been achieved from an optically active known diol through eight steps. The key transformations for the synthesis of PlsEtn-[16:0/18:1 n-9] are, (1) regio- and Z-selective vinyl ether formation via alkylation of a lithioalkoxy allyl intermediate with an alkyl iodide, and (2) a one-pot phosphite esterification–oxidation sequence to construct the ethanolamine phosphonate moiety in the presence of the vinyl ether functionality. The piperidine salt of synthetic PlsEtn-[16:0/18:1 n-9] was desalinated through reversed-phase HPLC purification.

Asymmetric Synthesis of α-Alkylated γ-Lactam via Nickel/8-Quinim-Catalyzed Reductive Alkyl-Carbamoylation of Unactivated Alkene

Chiral-auxiliary-mediated synthesis represents the most frequently used synthetic tool for the induction of chirality on α-position of γ-lactams in organic synthesis. However, the general strategy requires the stoichiometric use of chiral reagents with multiple manipulation steps. Transition-metal-catalyzed asymmetric alkene dicarbofunctionalization using readily available substrates under mild conditions allows the simultaneous construction of two vicinal chemical bonds and a chiral carbon center, hence, gain expedient access to chiral heterocycles. Herein, we disclose a Ni-catalyzed enantioselective reaction of 3-butenyl carbamoyl chloride and primary alkyl iodide enabled by a newly designed chiral 8-quinoline imidazoline ligand (8-Quinim). This protocol features broad functional group tolerance and high enantioselectivities, achieving unprecedented synthesis of chiral nonaromatic heterocycles via catalytic reductive protocol.1 Introduction2 Development of 8-Quinim Ligand3 Nickel/8-Quinim-Catalyzed Enantioselective Synthesis of Chiral α-Alkylated γ-Lactam4 Conclusion and Outlook

Radical Hydroxymethylation of Alkyl Iodides Using Formaldehyde as a C1 Synthon

Radical hydroxymethylation using formaldehyde as a C1 synthon is challenging due to the reversible and endothermic nature of the addition process. Here we report a strategy that couples alkyl iodide...

Reductive Ni-Catalysis for Stereoselective Carboarylation of Terminal Aryl Alkynes

Stereoselective dicarbofunctionalization of terminal aryl alkynes has been achieved through reductive Ni-catalysis. The exclusive regioselective and anti-addition selective alkylarylation of terminal alkynes is accomplished using alkyl iodide and aryl iodide...

Hydrogen bond cross-linked luminescent supramolecular network polymer and its application for detection of alkyl iodide with differentiation capabilities from aromatic iodide

Here, we have demonstrated a luminescent network polymer through H-bonds cross-linking strategy by connecting poly (4-vinyl pyridine) chains with perylene diimide (PDI) cross-linker. The formation of network structure through hydrogen...

Triphenylphosphine-catalyzed Alkylative Iododecarboxylation with Lithium Iodide under Visible Light

Photoactivation of an electron donor–acceptor encounter complex in an organic solvent cage, a phenomenon that has been described in Mulliken theory, has been known for decades, but it has not been employed as a photoactivation step in the design of photocatalysis for organic synthesis until recent years. We report herein an iododecarboxylation reaction that applies this concept for photoactivation by using a catalyst to facilitate electron transfer and to suppress back electron transfer in the photoexcited state. Under irradiation of 456 nm blue light-emitting diodes, PPh3 catalyzes the iododecarboxylation of aliphatic carboxylic acid-derived N-(acyloxy)phthalimide with lithium iodide as iodine source. The reaction delivers primary, secondary, and bridgehead tertiary alkyl iodides in acetone solvent, and the alkyl iodide products were easily used to generate C–N, C–O, C–F, and C–S bonds to allow various decarboxylative transformations without using transition-metal or organic dye-based photocatalysts. This protocol is applicable to redox-active esters derived from various natural products and pharmaceuticals.

Activation of Leukopoiesis in Rat Blood with Trimecaine-Based Ionic Compounds

A study of myelostimulating activity of ionic compounds-trimecaine alkyl iodide derivatives under the cipher BIV (BIV-117, BIV-118, and BIV-119) was conducted on a model of doxorubicin pancytopenia in white laboratory rats. It was established that the compounds BIV-117 and BIV-119 had a pronounced leukopoiesis-stimulating activity, exceeding the activity of the methyluracil as a comparison drug. Compounds BIV-117 and BIV-119 had erythropoiesis- and thrombocytopoiesis-stimulating activity at the level of methyluracil.