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31.
A new method is reported for the chirospecific preparation of optically pure 1-carboxy-7-azabicycloheptane amino acids for the generation of peptidomimetics as conformational probes. The method allows for the multigram preparation of these amino acid analogues through use of a thiolactam sulfide contraction and a transannular alkylation sequence as the key C-C bond-forming steps, starting from L-glutamic acid. The route provides access to two common intermediates, 7-(benzyloxycarbonyl)-1-carboxy-7-azabicyclo[2.2.1]-3-heptane and (1S,4R)-7-(benzyloxycarbonyl)-1-carboxy-7-azabicyclo[2.2.1]-3-heptanone tert-butyl ester, for elaboration to symmetrical and chiral amino acid homologues, respectively. Decarboxylation of the C-1 carboxy unit of the latter intermediate also demonstrated the applicability of the method for a short, chirospecific preparation of a (+)-epibatidine intermediate, (1S,4R)-7-(tert-butyloxycarbonyl)-1-carboxy-7-azabicyclo[2.2.1]-3-heptanone. 相似文献
32.
Tuo Jiang Samuele Bordi Angus E. McMillan Kuang-Yen Chen Fumito Saito Paula L. Nichols Benedikt M. Wanner Jeffrey W. Bode 《Chemical science》2021,12(20):6977
The current laboratory practices of organic synthesis are labor intensive, impose safety and environmental hazards, and hamper the implementation of artificial intelligence guided drug discovery. Using a combination of reagent design, hardware engineering, and a simple operating system we provide an instrument capable of executing complex organic reactions with prepacked capsules. The machine conducts coupling reactions and delivers the purified products with minimal user involvement. Two desirable reaction classes – the synthesis of saturated N-heterocycles and reductive amination – were implemented, along with multi-step sequences that provide drug-like organic molecules in a fully automated manner. We envision that this system will serve as a console for developers to provide synthetic methods as integrated, user-friendly packages for conducting organic synthesis in a safe and convenient fashion.Using a combination of reagent design, hardware engineering, and a simple operating system we provide an instrument capable of executing complex organic reactions using prepacked capsules with minimal user involvement. 相似文献
33.
Gregory M. Su Han Wang Brandon R. Barnett Jeffrey R. Long David Prendergast Walter S. Drisdell 《Chemical science》2021,12(6):2156
Metal–organic frameworks are promising materials for applications such as gas capture, separation, and storage, due to their ability to selectively adsorb small molecules. The metal–organic framework CuI-MFU-4l, which contains coordinatively unsaturated copper(i) centers, can engage in backbonding interactions with various small molecule guests, motivating the design of frameworks that engage in backbonding and other electronic interactions for highly efficient and selective adsorption. Here, we examine several gases expected to bind to the open copper(i) sites in CuI-MFU-4l via different electronic interactions, including σ-donation, π-backbonding, and formal electron transfer. We show that in situ Cu L-edge near edge X-ray absorption fine structure (NEXAFS) spectroscopy can elucidate π-backbonding by directly probing excitations to unoccupied backbonding orbitals with Cu d-character, even for gases that participate in other dominant interactions, such as ligand-to-metal σ-donation. First-principles calculations based on density functional theory and time-dependent density functional theory additionally reveal the backbonding molecular orbitals associated with these spectroscopic transitions. The energies of the transitions correlate with the energy levels of the isolated small molecule adsorbates, and the transition intensities are proportional to the binding energies of the guest molecules within CuI-MFU-4l. By elucidating the molecular and electronic structure origins of backbonding interactions between electron rich metal centers in metal–organic frameworks and small molecule guests, it is possible to develop guidelines for further molecular-level design of solid-state adsorbents for energy-efficient separations of relevance to industry. In situ near edge X-ray absorption fine structure spectroscopy directly probes unoccupied states associated with backbonding interactions between the open metal site in a metal–organic framework and various small molecule guests. 相似文献
34.
35.
Sammelson RE Gurusinghe CD Kurth JM Olmstead MM Kurth MJ 《The Journal of organic chemistry》2002,67(3):876-882
An efficient and selective method for the synthesis of spiro-fused (C5)-isoxazolino-(C4)-pyrazolones (C) is reported. The process consists of utilizing the Baylis-Hillman reaction-or a quicker, stepwise MAC procedure-to give I followed by 1,3-dipolar cycloaddition and Swern oxidation to give beta-ketoesters H, which were condensed with hydrazine derivatives to provide hydrazones that underwent cycloelimination. These novel spiro-fused (C5)-isoxazolino-(C4)-pyrazolones were confirmed by spectroscopic analysis as well as single-crystal X-ray of 5. We also concluded that all condensations/cycloeliminations, except with hydrazine itself, were more effective with catalysts or higher reaction temperatures. For example, TiCl(4) was an efficient catalyst for hydrazone formation and cycloelimination with methylhydrazine, while phenyl-, benzyl-, and (4-methoxyphenyl)hydrazine reacted effectively without catalyst in refluxing xylene. 相似文献
36.
Plunkett KN Mohraz A Haasch RT Lewis JA Moore JS 《Journal of the American Chemical Society》2005,127(42):14574-14575
The net charge of a colloidal particle was controlled using light and a new photocleavable self-assembled monolayer (SAM). The SAM contained a terminal ammonium group and a centrally located carboxylic acid group that was masked with an ortho-nitrobenzyl functionality. Once exposed to UV light, the 2-nitrobenzyl group was cleaved, therefore transforming the colloidal particle from a net positive (silica-SAM-NH3+) to a net negative (silica-SAM-COO-) charge. By varying the UV exposure time, their zeta potential could be tailored between +26 and -60 mV at neutral pH. To demonstrate a photoinduced gel-to-fluid phase transition, a binary colloidal suspension composed of silica-SAM-NH3+ and negatively charged, rhodamine-labeled silica particles was mixed to form a gel. Exposure to UV light rendered all of the particles negative and therefore converted the system into a colloidal fluid that settles to form a dense sediment. 相似文献
37.
The synthesis of 2-methyl-5H-dibenz[b,f]azepine-5-carboxamide (2-methylcarbamazepine, 2-MCBZ, 8), a promising internal standard for chromatographic assays of the antiepileptic agent carbamazepine (CBZ, 1), is described. N-(p-Tolyl)anthranilic acid (2) was utilized as a starting material for the synthesis of a key compound, 2,9-dimethylacridine (4), which was converted in two steps to 2-methyl-9-hydroxymethylacridan (6). The acridan 6, in the presence of poly-phosphoric acid, was ring-expanded to form 2-methyl-5H-dibenz[b,f]azepine (7), this latter compound being converted by conventional reactions to its 5-carbamyl derivative, 2-MCBZ (8). 相似文献
38.
Multiple oxidants have been implicated as playing a role in cytochrome P450-mediated oxidations. Herein, we report results on N-dealkylation, one of the most facile reactions mediated by P450 enzymes. We have employed the N-oxides of a series of para-substituted 13C2H2-labeled N,N-dimethylanilines to function as both substrates and surrogate oxygen atom donors for P450cam and P4502E1. Kinetic isotope effect profiles obtained using the N-oxide system were found to closely match the profiles produced using the complete NAD(P)H/NAD(P)-P450 reductase/O2 system. The results are consistent with oxidation occurring solely through an iron-oxene species. 相似文献
39.
A phase transition in NaOD has been observed calorimetrically near 150 K. The estimated enthalpy of the transition is 200(75) . This phase transition has no corresponding analog in the protonated material, NaOH, down to 10 K. Other physical techniques also reveal the phase transition but give slightly varying values for the transition temperature. These techniques include 23Na nuclear quadrupole resonance, 23Na nuclear magnetic resonance and 2D magnetic resonance. The resonance experiments indicate that the phase transition is a continuous one and that in the lower temperature phase there is one sodium and deuterium crystal Iographic site per cell. X-ray powder diffraction of the low temperature phase indicates that it is probably monoclinic with am = 3.388(1)A, bm = 11.34(1)A, cm = 3.418(1)A,β = 90.52° and V = 131 .4Å3. The volume of the unit cell is greater at the lower temperature than at the higher temperature. The 23Na pure quadrupole resonance frequency at 77 K is 1.784(2) MHz with an asymmetry parameter of 0.82(5). 相似文献
40.
The reaction of phenyl lithium acetylide () with 2,6-diphenylpyrylium perchlorate () is solvent dependent. With diethyl ether as solvent, the isolated product differed from that previously reported and is reassingned as 2,6-diphenyl-4-phenylacetylenyl-4-pyran (). On the other hand, in THF the title compound () was obtained; its structure confirmed by single-crystal x-ray crystallography. 相似文献