Structure-reactivity Relationships Research Articles

Global Optimization of Molybdenum Subnanoclusters on Graphene: A Consistent Approach toward Catalytic Applications.

The development of novel subnanometer clusters (SNCs) catalysts with superior catalytic performance depends on the precise control of clusters' atomistic sizes, shapes, and accurate deposition onto surfaces. The intrinsic complexity of the adsorption process complicates the ability to achieve an atomistic understanding of the most relevant structure-reactivity relationships hampering the rational design of novel catalytic materials. In most cases, existing computational approaches rely on just a few structures to draw conclusions on clusters' reactivity thereby neglecting the complexity of the existing energy landscapes thus leading to insufficient sampling and, most likely, unreliable predictions. Moreover, modeling of the actual experimental procedure that is responsible for the deposition of SNCs on surfaces is often not done even though in some cases this procedure may enhance the significance of certain (e.g., metastable) adsorption geometries. This study proposes a novel systematic approach that utilizes global search techniques, specifically, the particle swarm optimization (PSO) method, in conjunction with ab initio calculations, to simulate all stages in the beam experiments, from predicting the most relevant SNCs structures in the beam and on a surface, to their reactivity. To illustrate the main steps of our approach, we consider the deposition of Molybdenum SNC of 6 Mo atoms on a free-standing graphene surface, as well as their catalytic properties with respect to the CO molecule dissociation reaction. Even though our calculations are not exhaustive and serve only to produce an illustration of the method, they are still able to provide insight into the complicated energy landscape of Mo SNCs on graphene demonstrating the catalytic activity of Mo SNCs and the importance of performing statistical sampling of available configurations. This study establishes a reliable procedure for performing theoretical rational design predictions.

Studying the Photoactivity of Ag-Decorated TiO2 Nanotubes with Combined AFM and Raman Spectroscopy

The drive for the development of systems that can simultaneously investigate chemical and morphological information comes from the requisite to fully understand the structure and chemical reactivity relationships of materials. This is particularly relevant in photocatalysis, a field ruled by surface interactions. An in-depth understanding of these complex interactions could lead to significant improvements in materials design, and consequently, in photocatalytic performances. Here, we present a first approach to a combined atomic force microscopy (AFM) and Raman spectroscopy characterization of anodic TiO2 nanotubes arrays decorated with Ag nanoparticle electrodeposition from either the same anodizing organic electrolyte or from an aqueous one. Photocatalytic substrates were used in up to 15 consecutive photocatalysis tests to prove their possible deterioration with reuse. Sample aging can, in principle, produce changes in both the morphology and the chemical compounds that characterize the photocatalyst surface. Adopting multiple characterization techniques, such as a combination of AFM and Raman spectroscopy in an original setup, can profitably enable the observation of surface contamination. A significant drop in photocatalytic activity was observed after 10 cycles on samples where silver was deposited from the organic electrolyte, while the others remained stable. Such a drop was ascribed to photocatalyst deactivation. While in other cases, a simple recovery treatment allowed the initial photoactivity to be restored, this deactivation was not restored even after chemical and thermal cleaning treatments.

Structure–reactivity relationships in the removal efficiency of catechol and hydroquinone by structurally diverse Mn-oxides

Catechol and hydroquinone are widely present hydroxybenzene isomers in the natural environment that induce environmental toxicities. These hydroxybenzene compounds can be effectively removed by manganese (Mn)-oxides via sorption and oxidative degradation processes. In the present study, we investigated the structure–reactivity relationships in the sorption and oxidation of catechol and hydroquinone on Mn-oxide surfaces. Two widely present Mn-oxides, including hydrous Mn oxide (HMO) and cryptomelane, comprised of layer and tunnel structures, respectively, are specifically studied. Effects of Mn-oxide structures and environmental pH conditions on the removal efficiency of these hydroxybenzene compounds, via sorption and oxidative degradation, are investigated. Cryptomelane, which has a higher specific surface area than HMO, possesses a higher sorption and oxidation capacity. The complexation mechanisms of catechol and hydroquinone vary due to their structure-induced difference in reactivity. Catechol reduced and dissolved more Mn from Mn-oxides than hydroquinone, accompanied by a higher C loss of catechol-C, suggesting a higher reactivity of catechol. Structural changes occurred in the Mn-oxides resulting from reaction with catechol and hydroquinone: reduction of Mn(IV), corresponding formation of Mn(III) and Mn(II) in the mineral, and free Mn2+ ions released into the suspension. These insights could help us better understand and predict the fate of hydroxybenzene compounds in Mn-oxide-rich soils and wastewater treatment systems that generate Mn-oxides via Mn removal and the associated environmental toxicity.

Computational Study of SmI2-Catalyzed Intermolecular Couplings of Cyclopropyl Ketones: Links between the Structure and Reactivity.

SmI2-catalyzed intermolecular coupling reactions of cyclopropyl ketones with alkenes or alkynes offer an efficient strategy for furnishing diverse five-membered ring-containing molecular architectures. This study presents a systematic computational investigation to reveal the structure-reactivity relationships in these reactions. The reactivity of aryl cyclopropyl ketones is enhanced by the stabilized ketyl radical and cyclopropyl fragmentation, arising from the conjugation effect of the aryl ring, despite an obstacle emerging from the gauche styrene intermediate that elevates the energy barrier for radical trapping. By contrast, alkyl cyclopropyl ketones lack conjugation and exhibit high barriers for reduction and fragmentation but undergo facile radical trapping due to the minimal steric hindrance. Interestingly, ortho-substituted phenyl cyclopropyl ketones exhibit superior reactivity due to a balance between the moderate conjugation, promoting cyclopropyl fragmentation, and the pretwisted nature of the ortho-substituted phenyl that circumvents the hindrance posed by the gauche intermediate and facilitates the radical trapping. The markedly enhanced reactivity of bicyclo[1.1.0]butyl (BCB) ketones arises from facile fragmentation of the strained BCB motif. Bicyclo[2.1.0]pentyl (BCP) ketones, less strained than BCB ketones, are computationally verified to undergo efficient couplings with various partners, and this can be attributed to their stable fragmentation intermediates that facilitate radical trapping. Our findings provide insights that can aid in designing related reactions.

Surface Chemical Effects on Fischer–Tropsch Iron Oxide Catalysts Caused by Alkali Ion (Li, Na, K, Cs) Doping

Among the alkali metals, potassium is known to significantly shift selectivity toward value-added, heavier alkanes and olefins in iron-based Fischer–Tropsch synthesis catalysts. The aim of the present contribution is to shed light on the mechanism of action of alkaline promoters through a systematic study of the structure–reactivity relationships of a series of Fe oxide FTS catalysts promoted with Group I (Li, Na, K, Cs) alkali elements. Reactivity data are compared to structural data based on in situ, synchrotron-based XRD and XPS, as well as temperature-programmed studies (TPR-H2, TPC-CO, TPD-CO2, and TPD-H). It has been observed that the alkali elements induced higher carburization rates, higher basicities, and lower adsorbed hydrogen coverages. Catalyst stability followed the trend Na-Fe > unpromoted > Li-Fe > K-Fe > Cs-Fe, being consistent with the ability of the alkali (Na) to prevent active site loss by catalyst reoxidation. Potassium was the most active in promoting high α hydrocarbon formation. It is active enough to promote CO dissociative adsorption (and the formation of FeCx active phases) and decrease the surface coverage of H-adsorbed species, but it is not so active as to cause premature catalyst deactivation by the formation of a carbon layer resulting in the blocking active sites.

Structure-Reactivity Relationships in a Small Library of Imine-Type Dynamic Covalent Materials: Determination of Rate and Equilibrium Constants Enables Model Prediction and Validation of a Unique Mechanical Softening in Dynamic Hydrogels.

The development of next generation soft and recyclable materials prominently features dynamic (reversible) chemistries such as host-guest, supramolecular, and dynamic covalent. Dynamic systems enable injectability, reprocessability, and time-dependent mechanical properties. These properties arise from the inherent relationship between the rate and equilibrium constants (RECs) of molecular junctions (cross-links) and the resulting macroscopic behavior of dynamic networks. However, few examples explicitly measure RECs while exploring this connection between molecular and material properties, particularly for polymeric hydrogel systems. Here we use dynamic covalent imine formation to study how single-point compositional changes in NH2-terminated nucleophiles affect binding constants and resulting hydrogel mechanical properties. We explored both model small molecule studies and model polymeric macromers, and found >3-decade change in RECs. Leveraging established relationships in the literature, we then developed a simple model to describe the cross-linking equilibrium and predict changes in hydrogel mechanical properties. Interestingly, we observed that a narrow ≈2-decade range of Keq's determine the bound fraction of imines. Our model allowed us to uncover a regime where adding cross-linker before saturation can decrease the cross-link density of a hydrogel. We then demonstrated the veracity of this predicted behavior experimentally. Notably this emergent behavior is not accounted for in covalent hydrogel theory. This study expands upon structure-reactivity relationships for imine formation, highlighting how quantitative determination of RECs facilitates predicting macroscopic behavior. Furthermore, while the present study focuses on dynamic covalent imine formation, the underlying principles of this work are applicable to the general bottom-up design of soft and recyclable dynamic materials.

Role of Solvent and Noncovalent Interactions in Alkaline Reactivity of Strained and Strain-Free Macrocyclic Disulfides.

This study employs ab initiomolecular dynamics simulations to investigate the impact of solvent and non-bonded interactions on the structure-reactivity relationship of both strain-free and strained macrocyclic disulfides. Our findings reveal that interactions with water as a solvent significantly influence the minimum energy geometry structures of both conformers of the studied macrocycle. In particular, our simulations identify short contacts, specifically S···π-aromatic interactions, which suppress reactivity for the strained isomer by obstructing the reaction cone at the minimum free energy. Surprisingly, the free energy barriers for the disulfide reaction with a simple nucleophile (OH-anion) remain very similar, despite one conformer having a markedly more strained disulfide bond than the other. Enhanced molecular dynamics simulations in explicit solution elucidate this apparent contradiction by revealing different solvent exposures of the two sulfur atoms in the macrocycles.

Origins of enhanced oxygen reduction activity of transition metal nitrides.

Transition metal nitride (TMN-) based materials have recently emerged as promising non-precious-metal-containing electrocatalysts for the oxygen reduction reaction (ORR) in alkaline media. However, the lack of fundamental understanding of the oxide surface has limited insights into structure-(re)activity relationships and rational catalyst design. Here we demonstrate how a well-defined TMN can dictate/control the as-formed oxide surface and the resulting ORR electrocatalytic activity. Structural characterization of MnN nanocuboids revealed that an electrocatalytically active Mn3O4 shell grew epitaxially on the MnN core, with an expansive strain along the [010] direction to the surface Mn3O4. The strained Mn3O4 shell on the MnN core exhibited an intrinsic activity that was over 300% higher than that of pure Mn3O4. A combined electrochemical and computational investigation indicated/suggested that the enhancement probably originates from a more hydroxylated oxide surface resulting from the expansive strain. This work establishes a clear and definitive atomistic picture of the nitride/oxide interface and provides a comprehensive mechanistic understanding of the structure-reactivity relationship in TMNs, critical for other catalytic interfaces for different electrochemical processes.

Different Reaction Mechanisms Triggered by the Meta Effect: Photoinduced Generation of Quinone Methides from Hydroxybiphenyl Derivatives.

A series of sterically congested quinone methides (QMs) exhibit photoinduced antiproliferative activity against some human cancer cell lines. To elucidate the structure-reactivity relationship and details of mechanisms of the photogeneration of sterically congested QMs, we chose phenylphenol derivatives 1-3 as QM precursors and investigated their photodehydration processes in aqueous solutions using ultrafast spectroscopy and theoretical computations. We found that meta derivatives 1 and 2 undergo water-mediated excited-state proton transfer (ESPT) from the phenol OH, followed by expulsion of the OH- to form QMs. By comparison, para derivative 3 proceeds via water-mediated ESPT from H2O to benzyl alcohol coupled with dehydration as the first step, delivering a cation intermediate, which further deprotonates to yield QM. Such results would help chemists understand more about the meta effects in photochemistry and about ESPT and would help synthetic chemists design sterically congested QM precursors with extraordinary reactivities and expand applications of QMs in biological and medical systems.

(Invited) Design of Photoactive Inorganic Nanomaterials for Environmental Challenges

Nowadays, one of the main technological challenges that we are facing is the ability to provide a sustainable supply of clean energy and, among all renewable sources, solar energy displays the greatest potential. Recently, the development of novel synthetic strategies has led to the preparation of nanostructured materials displaying unique properties compared to the bulk counterpart systems, with controlled and tunable morphologies able to enhance the activity and selectivity of a catalytic process. In particular, nanostructured materials synthesized via the bottom–up approach present an opportunity for future generation manufacturing of devices.This talk will focus on the importance of tuning the morphological features of a catalyst as a strategy to improve its optical and photocatalytic properties, focusing on how rationally designing inorganic materials at the nanoscale can lead to morphologies and structures suitable to enhance the performance of industrially and environmentally important processes. The talk will discuss some environmental applications that can be addressed by photoactive multi-component oxide systems synthesized via the bottom–up approach, highlighting their structure-reactivity relationship. Water contamination, in particular, is one of the upfront issues to be solved and complex organic molecules and pharmaceuticals, including antibiotics, are gaining attention due to their abuse and their low degradability. Photocatalytic drugs degradation will be presented as a successful case history [1-3] to provide inspiration to produce cheap, environmentally friendly, stable, and efficient photocatalysts, which hold a great potential for the development of new technologies not only for water remediation applications but also for energy applications in the field of solar fuel production.[1] E. Moretti, L. Storaro, A. Talon, P. Riello, A. Infantes Molina, E. Rodríguez-Castellón, Appl. Catal. B: Environmental 168 (2015) 385.[2] M. Telkhozhayeva, B. Hirsch, R. Konar, E. Teblum, R. Lavi, M. Weitman, B. Malik, E. Moretti, G.D. Nessim, Appl. Catal. B: Environmental 318 (2022) 121872.[3] L. Liccardo, M. Bordin, P.M. Sheverdyaeva, M. Belli, P. Moras, A. Vomiero, E. Moretti, Adv. Funct. Mater. 33 (2023) 2212486.

Integrating Polyoxometalates and Silver Clusters into Atomically Precise Molecular Heterojunction.

The Ag cluster-POM assemblies have been shown to possess interesting and potentially useful properties. However, there is no precedent example of atomically precise Ag cluster-POM assemblies showing heterojunction effects in photocatalysis. Herein, the synthesis and total structure determination of the periodically distributed molecular heterojunction [Ag12(SCy)6(CH3CN)12(PW12O40)]n (Ag12-PW12) are reported. The assembly of Ag/W clusters into 3D network can endow the resulting binary structure with an aesthetic topology and unique physicochemical properties. More remarkably, the incorporation of Ag12 cluster with PW12 can efficiently facilitate the separation of photogenerated electrons and holes, thus significantly promoting the catalytic efficiency in selective oxidation of sulfides. The Ag12-PW12 heterojunction can be recovered and reused five times with no drastic change in the catalytic performance. This research is expected to assist in the rational design of cluster-based heterojunction catalysts. The increase of catalytic activity of the Ag12-PW12 assembly in comparison with the unassembled Ag12 and PW12 clusters is attributed to the synergistic effect of Ag12 and PW12 clusters, offering the splendid opportunity for deciphering structure-reactivity relationship of heterostructure-coupled photosystem.

Experimentally validating sabatier plot by molecular level microenvironment customization for oxygen electroreduction

Microenvironmental modifications on metal sites are crucial to tune oxygen reduction catalytic behavior and decrypt intrinsic mechanism, whereas the stochastic properties of traditional pyrolyzed single-atom catalysts induce vague recognition on structure-reactivity relations. Herein, we report a theoretical descriptor relying on binding energies of oxygen adsorbates and directly associating the derived Sabatier volcano plot with calculated overpotential to forecast catalytic efficiency of cobalt porphyrin. This Sabatier volcano plot instructs that electron-withdrawing substituents mitigate the over-strong *OH intermediate adsorption by virtue of the decreased proportion of electrons in bonding orbital. To experimentally validate this speculation, we implement a secondary sphere microenvironment customization strategy on cobalt porphyrin-based polymer nanocomposite analogs. Systematic X-ray spectroscopic and in situ electrochemical characterizations capture the pronounced accessible active site density and the fast interfacial/outward charge migration kinetics contributions for the optimal carboxyl group-substituted catalyst. This work offers ample strategies for designing single-atom catalysts with well-managed microenvironment under the guidance of Sabatier volcano map.

Synthetic Mn3Ce2O5-Cluster Mimicking the Oxygen-Evolving Center in Photosynthesis.

The photosynthetic oxygen-evolving center (OEC) is a unique Mn4CaO5-cluster that catalyses water splitting into electrons, protons, and dioxygen. Precisely structural and functional mimicking of the OEC is a long-standing challenge and pressingly needed for understanding the structure-function relationship and catalytic mechanism of O-O bond formation. Herein we report two simple and robust artificial Mn3Ce2O5-complexes that display a remarkable structural similarity to the OEC in regarding of the ten-atom core (five metal ions and five oxygen bridges) and the alkyl carboxylate peripheral ligands. This Mn3Ce2O5-cluster can catalyse the water-splitting reaction on the surface of ITO electrode. These results clearly show that cerium can structurally and functionally replace both calcium and manganese in the cluster. Mass spectroscopic measurements demonstrate that the oxide bridges in the cluster are exchangeable and can be rapidly replaced by the isotopic oxygen of H2 18O in acetonitrile solution, which supports that the oxide bridge(s) may serve as the active site for the formation of O-O bond during the water-splitting reaction. These results would contribute to our understanding of the structure-reactivity relationship of both natural and artificial clusters and shed new light on the development of efficient water-splitting catalysts in artificial photosynthesis.

Reactivity of diethyl benzylidenemalonates with secondary cyclic amine dimers in acetonitrile: Structure-reactivity relationships and mechanism

We report on a kinetic study for the nucleophilic addition reactions of diethyl 4-X-substituted benzylidenemalonates 1a-c (X = N(CH3)2, OCH3 and CH3) with N-nucleophiles, such as morpholine 2a, piperidine 2b and pyrrolidine 2c by UV–vis spectroscopy in acetonitrile solution at 20 °C. The Hammett plots demonstrate much better linear correlations with σp+ constants than with σp constants. These results are best interpreted in terms of ground state stabilization through resonance interactions between the electron-donating substituent and the CO2Et group. The effect of amine basicity on the reaction rate was examined quantitatively, leading to linear correlations with high βnuc values in the 0.82–0.93 range. The origin of the abnormally high βnuc values was interpreted in terms of dimer mechanism. Finally, with the help of our new proposed linear free energy relationship log k1K (20 °C) = sN (E + N) + log K, the stability of the dimer amines (K) have been evaluated from the measured apparent second-order rate constant (k1K) and the previously reported E, N and sN parameters of the employed electrophiles 1a-c and nucleophiles 2a-c. Additionally, a complementary theoretical study utilizing Density Functional Theory (DFT) with the B3LYP/6-311g(d,p) method was conducted in acetonitrile. An attempt is made to establish the correlation between equilibrium constant and stabilization energy the studied systems.

Studying the Intrinsic Reactivity of Chromanes by Gas-Phase Infrared Spectroscopy.

Tandem mass spectrometry is routinely used for the structural analysis of organic molecules, but many fragmentation reactions are not well understood. Because several potential structures can correspond to a measured mass, the assignment of product ions is ambiguous using mass spectrometry alone. Here, we combine mass spectrometry with high-resolution gas-phase infrared spectroscopy and computational chemistry tools to identify product ion structures and derive collision-induced fragmentation mechanisms of the chromane derivatives Trolox and Methyltrolox. We find that protonated Trolox and Methyltrolox fragment identically via dehydration and decarbonylation, while deprotonated ions display substantially diverging reactivities. For deprotonated Methyltrolox, we observe unusual radical fragmentation reactions and suggest a [1,2]-Wittig rearrangement involving aryl migration in the gas phase. Overall, the combined experimental and theoretical approach presented here revealed complex proton dynamics and intramolecular rearrangement reactions, which expand our understanding on structure-reactivity relationships of isolated molecules in different protonation states.

Deconstruction of Polymers through Olefin Metathesis.

The consumption of synthetic polymers has ballooned; so has the amount of post-consumer waste generated. The current polymer economy, however, is largely linear with most of the post-consumer waste being either landfilled or incinerated. The lack of recycling, together with the sizable carbon footprint of the polymer industry, has led to major negative environmental impacts. Over the past few years, chemical recycling technologies have gained significant traction as a possible technological route to tackle these challenges. In this regard, olefin metathesis, with its versatility and ease of operation, has emerged as an attractive tool. Here, we discuss the developments in olefin-metathesis-based chemical recycling technologies, including the development of new materials and the application of olefin metathesis to the recycling of commercial materials. We delve into structure-reactivity relationships in the context of polymerization-depolymerization behavior, how experimental conditions influence deconstruction outcomes, and the reaction pathways underlying these approaches. We also look at the current hurdles in adopting these technologies and relevant future directions for the field.

Reactivity-based detection of nitrite ion: Rapid colorimetric and fluorometric response down to nM level

Recent developments in our lab provided significant insight into the structure–reactivity relationship between electronic properties and the detection of nitrite ions. By fine-tuning electron-withdrawing and electron-donating power, the sulfonamide group on aniline moiety was found to be the fastest nitrite probe among the first generation of probe molecules. Based on our understanding of the detection mechanism, our attention was moved to additional modification by installing stronger electron-donating groups on the azo-coupling partner. Accordingly, the bis methoxy group version of the probe molecule was prepared. It showed clean conversion from the probe to the benzo[c]cinnoline product and excellent linear response to very low levels of nitrite ions. Proton NMR and high-resolution mass spectrometer captured the reaction between the probe molecule and nitrite ions. As the reaction with nitrite ion triggers diazonium intermediate formation followed by intramolecular cyclization, both absorption and emission property changes were monitored as the signal readout to assay nitrite ion. In this report, our design principle of a probe molecule and its performance in colorimetric and fluorimetric responses will be discussed. In addition, the low detection limit achieved by leveraging chromatographic separation and assaying by the mass detector will be discussed.

N-Butyltin(IV) trichloride initiator for the solvent-free ring-opening polymerization of ε-caprolactone: evaluation of the structure-reactivity relationship of tin(IV) derivatives

n-Butyltin(IV) trichloride initiator for the solvent-free ring-opening polymerization of ε-caprolactone: evaluation of the structure-reactivity relationship of tin(IV) derivatives

Highlighting the “structure–reactivity” relationship and the impact on the kinetics for the autoxidation reaction of hydrocarbons

The interactions between heteroatomic species and the hydrocarbons present in Jet A-1 make the determination of degradation mechanisms difficult to elucidate and predict. This study aims to investigate the reaction mechanisms and kinetics of hydrocarbon molecules constituting jet fuel, excluding molecules with polar species. Five model hydrocarbons were selected (n-dodecane and its isomeric mixture, n-butylcyclohexane, 1,2,4-trimethylbenzene and 1-methylnaphthalene) and individually subjected to oxidation using the PetroOXY apparatus, focusing on the onset of autoxidation (ΔP/Pmax = 2 to 10 %). For the first time, an experimental protocol has been developed for the monitoring of gas and liquid phase reagent consumption and the identification and quantification of oxidation products formed in these phases. The results showed that oxygen consumption was always higher than that of the initial hydrocarbons, suggesting competitive reactions, with alkanes consuming more oxygen than aromatic molecules, as confirmed by induction periods (IP), demonstrating the different reactivity depending on the structure of the oxidized hydrocarbon molecule. A relationship between initial hydrocarbon structure and the type and number of carbon atoms in oxidation products was also demonstrated. A gel, probably a precursor deposit, was obtained after oxidation of the molecules, indicating a potential precipitation of polar species due to the difference in polarity with the hydrocarbon molecules. In addition, the overall kinetic and hydroperoxide dissociation constants of the reaction could be calculated from tests carried out at different temperatures (140, 150 and 160 °C). The Arrhenius parameter values were higher for alkanes than for aromatics, confirming the structure–reactivity relationship of hydrocarbons. A strong correlation between the Arrhenius parameters and the nature of the oxidized molecules was also demonstrated. This experimental study will be useful for the calibration of future kinetic models according to the chemical structure of the oxidized hydrocarbons and for the assessment of thermal stability behavior of 100 % Synthetic Alternative Fuels (SAF).

Kinetic Resolution of Cyclic Tertiary Alcohols with Lipase A from Candida Antarctica

AbstractEnzyme‐catalyzed acylative kinetic resolution (KR) and dynamic kinetic resolution (DKR) of racemic primary and secondary alcohols have been widely reported to produce esters with high enantiomeric purity. In contrast, similar KRs of tertiary alcohols have been reported for only a limited range of substrates and require prolonged reaction times of several days. To gain deeper insight into the substrate scope and increase the process efficiency, we examined the reaction conditions using commercially available immobilized lipase A from Candida antarctica and found that the addition of the heterogeneous, inorganic base sodium carbonate significantly increased the reaction rate while maintaining high enantioselectivity. The use of vinyl hexanoate as the acyl donor provided esters that were stable during chromatography purification. The optimized reaction conditions were then successfully applied to a range of cyclic tertiary alcohols containing tetralin, dihydroindene, chromane, and thiochromane skeletons having, in part, a substituent on the aromatic ring. In this study on the structure–reactivity relationship of enzymatic KR‐type reactions, we achieved >30 % conversion for various tertiary alcohols in 24 h at 25 °C, producing optically active esters with 88–99 % ee.