ABSTRACT
A method for the synthesis of allenes by the addition of ketones to 1,3-enynes by cooperative Pd(0)Senphos/B(C6F5)3/NR3 catalysis is described. A wide range of aryl- and aliphatic ketones undergo addition to various 1,3-enynes in high yields at room temperature. Mechanistic investigations revealed a rate-determining outer-sphere proton transfer mechanism, which was corroborated by DFT calculations.
ABSTRACT
The first aromatic Claisen rearrangement of a 1,2-azaborine is described along with a quantitative kinetic comparison of the reaction of the azaborine with its direct all-carbon analogue. The azaborine A rearranged in a clean, regioselective fashion and reacted faster than the all-carbon substrate B at all temperatures from 140-180 °C. Activation free energies were extracted from observed first-order rate constants (A: ΔG298K = 32.7 kcal mol-1; B: ΔG298K = 34.8 kcal mol-1) corresponding to a twenty fold faster rate for A at observed reaction temperatures. DFT calculations show that the rearrangement proceeds via a concerted six-membered transition state and that the electronic structure of the BN and CC rings is mostly responsible for the observed regioselectivity and relative reactivity.
ABSTRACT
We report a combined experimental and computational study of Pd/Senphos-catalyzed carboboration of 1,3-enynes utilizing DFT calculations, 31P NMR study, kinetic study, Hammett analysis and Arrhenius/Eyring analysis. Our mechanistic study provides evidence against the conventional inner-sphere ß-migratory insertion mechanism. Instead, a syn outer-sphere oxidative addition mechanism featuring a Pd-π-allyl intermediate followed by coordination-assisted rearrangements is consistent with all the experimental observations.
ABSTRACT
The reaction mechanism of the Pd/Senphos-catalyzed trans-hydroboration reaction of 1,3-enynes was investigated using various experimental techniques, including deuterium and double crossover labeling experiments, X-ray crystallographic characterization of model reaction intermediates, and reaction progress kinetic analysis. Our experimental data are in support of an unusual outer-sphere oxidative addition mechanism where the catecholborane serves as a suitable electrophile to activate the Pd0-bound 1,3-enyne substrate to form a Pd-η3-π-allyl species, which has been determined to be the likely resting state of the catalytic cycle. Double crossover labeling of the catecholborane points toward a second role played by the borane as a hydride delivery shuttle. Density functional theory calculations reveal that the rate-limiting transition state of the reaction is the hydride abstraction by the catecholborane shuttle, which is consistent with the experimentally determined rate law: rate = k[enyne]0[borane]1[catalyst]1. The computed activation free energy ΔG = 17.7 kcal/mol and KIE (kH/kD = 1.3) are also in line with experimental observations. Overall, this work experimentally establishes Lewis acids such as catecholborane as viable electrophilic activators to engage in an outer-sphere oxidative addition reaction and points toward this underutilized mechanism as a general approach to activate unsaturated substrates.
ABSTRACT
Mechanistic details of cellulose depolymerization by non-thermal (atmospheric) plasma (NTAP) remains under-explored given the complexity of the medium. In this study, we have investigated the reaction mechanism of glycosidic-bond degradation triggered by reaction with hydroxyl radicals, considered as the principal reactive species in NTAP medium. In the first step of reaction sequence, H-abstraction reactions by HO⧠. radical on different CH sites of the pyranose ring were found to be non-selective and markedly exergonic giving rise to a set of cellobiosyl carboradicals likely to undergo further reactions. We then showed that cellobiosyl carboradicals are protected against direct hydrolysis, no activation of the (1-4)- ß -glycosidic bond being characterized. Interestingly, a simple homolytic bond cleavage allowed to obtain desired monomer. Among the 18 possible fragmentations, involving CC and CO bond breaking from cellobiosyl carboradicals, 14 transition states were successfully identified, and only three reaction pathways proved kinetically and thermodynamically feasible. Natural bond orbital (NBO) analysis was performed to shed light on electronic structures of different compounds.
Subject(s)
Cellulose , Hydroxyl Radical , Cellulose/chemistry , HydrolysisABSTRACT
A new family of carbon-bound boron enolates, generated by a kinetically controlled halogen exchange between chlorocatecholborane and silylketene acetals, is described. These C-boron enolates are demonstrated to activate 1,3-enyne substrates in the presence of a Pd0 /Senphos ligand complex, resulting in the first examples of a carboboration reaction of an alkyne with enolate-equivalent nucleophiles. Highly substituted dienyl boron building blocks are produced in excellent site-, regio-, and diastereoselectivity by the described catalytic cis-carboboration reaction.
ABSTRACT
A new Zn-N4 -Schiff base L=((±)-trans-N,N'-Bis(2-aminobenzylidene)-1,2-diaminocyclohexane) complex was synthesized and fully characterized, showing an unexpected self-assembled double-stranded helicate structure. The X-ray crystal analysis of the Zn2 L2 complex ((C40 H44 N8 Zn2 ,CH2 Cl2 , a=14.2375(3) Å, b=16.7976(4) Å, c=16.1613(4) Å, monoclinic, P21 /n, Z=4) shows a centrosymmetrical structure in which zinc atoms are in distorted tetrahedral environments, revealing an M- (R, R) left-handed helicity in its asymmetric unit. However, it was observed that this dinuclear complex is thermodynamically unstable in the presence of small water amounts and undergoes demetallation into free N4-Schiff base ligand and ZnO nanoparticles. This hydrolysis process was thoroughly identified and monitored through detailed 1 H NMR, DOSY NMR analysis. The reaction mechanism of this demetallation event was elucidated by using the DFT method, involving an activation energy smaller than 13â kcal/mol. Besides, a theoretical mechanism of the demetallation process is given for the first time.