Peter R Schreiner

Peter R Schreiner
Justus-Liebig-Universität Gießen | JLU · Institute of Organic Chemistry

Dr. rer. nat.; PhD

About

717
Publications
56,117
Reads
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22,213
Citations
Citations since 2016
222 Research Items
10637 Citations
201620172018201920202021202205001,0001,500
201620172018201920202021202205001,0001,500
201620172018201920202021202205001,0001,500
201620172018201920202021202205001,0001,500
Introduction
My research group is interested in understanding organic chemistry at its most fundamental level. This includes the preparation of previously unknown molecules through low temperature techniques (e.g., hydroxycarbenes), the introduction and use of hydrogen-bonding organocatalysts (mostly thioureas), and the development of the chemistry of nanodiamonds that nature graciously provides. We utilize combinations of chemical synthesis, spectroscopy and high-level computations for most of our projects.
Additional affiliations
March 2012 - March 2012
Technion - Israel Institute of Technology
Position
  • Schulich visiting professor
July 2002 - present
Justus-Liebig-Universität Gießen
Position
  • Full Professor of Chemistry
October 1996 - December 2000
Georg-August-Universität Göttingen
Position
  • Professor (Assistant)

Publications

Publications (717)
Article
Full-text available
1,2-Ethenediols are deemed key intermediates in prebiotic and interstellar syntheses of carbohydrates. Here we present the gas-phase synthesis of these enediols, the high-energy tautomers of glycolaldehyde, trapped in cryogenic argon matrices. Importantly, upon photolysis at ʎ = 180–254 nm, the enols rearrange to the simplest sugar glycolaldehyde.
Preprint
Full-text available
On-surface synthesis is at the verge of emerging as the method of choice for the generation and visualization of unstable or unconventional molecules, which could not be obtained via traditional synthetic methods. A case in point is the on-surface synthesis of the structurally elusive cyclotriphosphazene (P 3 N 3 ), an inorganic aromatic analogue o...
Article
We present an experimental and computational study to investigate noncovalent interactions between silyl groups that are often employed as “innocent” protecting groups. We chose an extended cyclooctatetraene (COT)-based molecular balance comprising unfolded (1,4-disubstituted) and folded (1,6-disubstituted) valance bond isomers that typically displ...
Article
We report a general and scalable method for the synthesis of all-meta-trisubstituted benzenes from readily available 3,5-disubstituted catechols. Oxidation and [4 + 2] cycloaddition with acetylene dienophiles generate a bicyclo[2.2.2]octane structure that is doubly decarbonylated initiated by blue-light irradiation, leading to a meta,meta-disubstit...
Article
We have conducted an experimental and computational study of cyclooctatetraene-1,4/1,6-dimethanol (1,4 and 1,6) as a molecular balance with the goal in mind to determine the otherwise inaccessible hydrogen bonding energy (HBE) of the cyclic water dimer, which constitutes a transition state. The 1,4/1,6 folding equilibrium is governed by an intramol...
Article
We present a combined experimental and computational study on the thermodynamic stability of cis- and trans-alkenes substituted with dispersion energy donor (DED) groups. To investigate the role of noncovalent interactions on equilibrium of cis- and trans-alkenes we utilized hydrochlorination reactions. While the general assumption is that increasi...
Article
The first bioinspired, enantioselective, and protecting group free total synthesis of the antibacterial sesquiterpenoid (-)-antroalbocin A (1) has been achieved in 12 steps (5.4% overall yield) from dimedone. An organocatalytic Robinson annulation gave rapid access to the tricyclic enone (19) as starting material for the photochemical domino proces...
Article
Accurate thermochemistry is essential in many chemical disciplines, such as astro-, atmospheric, or combustion chemistry. These areas often involve fleetingly existent intermediates whose thermochemistry is difficult to assess. Whenever direct calorimetric experiments are infeasible, accurate computational estimates of relative molecular energies a...
Article
Sustainable efficient light emitters based solely on elements-of-hope are needed to replace current compounds based on less-abundant materials. Functionalized diamondoids are a potential solution for this challenge, as a prototypical example offers efficient, octave-spanning emission across the visible spectrum in their single-crystalline form. Its...
Article
Certain adamantane (Ad)‐like molecules, either clusters of the type [(R′T) 4 E 6 ] with inorganic cores (R′ = cyclic/aromatic organic substituent; T = Si, Ge, Sn; E = S, Se, Te) or adamantane derivatives [(R′C) 4 (CH 2 ) 6 ] = R′ 4 Ad, display extreme nonlinear optical properties, which can lead to white‐light emission when exposed to near infrared...
Article
Full-text available
Room-temperature stable main group element carbonyl complexes are rare. Here we report on the synthesis of two such complexes, namely gallium-substituted silylene-carbonyl complexes [L(X)Ga]2SiCO (X = I 2, Me 3; L = HC[C(Me)NDipp]2, Dipp = 2,6-iPr2C6H3) by reaction of three equivalents of LGa with IDippSiI4 (IDipp = 1,3-bis(2,6-iPr2C6H3)-imidazol-2...
Article
We present a strategy for the skeletal editing of diamondoid structures to selectively displace methylene for heteroatom moieties in the carbon framework. This constitutes a synthetic approach to doping diamond-like structures with electron donor dopants (O, N, and S). The key steps involve two subsequent retro-Barbier fragmentations followed by ca...
Article
Full-text available
We present an experimental and computational study on the conformers of N , N ’‐diphenylthiourea substituted with different dispersion energy donor (DED) groups. While the unfolded anti − anti conformer is the most relevant for thiourea catalysis, intramolecular noncovalent interactions counterintuitively favor the folded syn − syn conformer, as ev...
Article
Full-text available
We present an experimental and computational study on the conformers of N , N ’‐diphenylthiourea substituted with different dispersion energy donor (DED) groups. While the unfolded anti − anti conformer is the most relevant for thiourea catalysis, intramolecular noncovalent interactions counterintuitively favor the folded syn − syn conformer, as ev...
Article
Full-text available
The rationalization of non‐covalent binding trends is both of fundamental interest and provides new design concepts for biomimetic molecular systems. Cucurbit[n]urils (CBn) are known for a long time as the strongest synthetic binders for a wide range of (bio)organic compounds in water. However, their host‐guest binding mechanism remains ambiguous d...
Preprint
Full-text available
Sustainable efficient light emitter based solely on elements-of-hope are needed to replace current compounds based on less-abundant materials. Functionalized diamondoids are a potential solution for this challenge as they offer efficient, octave-spanning emission across the visible spectrum in their single-crystalline form. Its large quantum effici...
Preprint
Functionalized adamantane molecular cluster materials show highly transient nonlinear optical properties of currently unclear structural origin. Several interaction mechanisms in compounds comprising molecular clusters, their inter- and intramolecular interactions as well as the interplay of their electronic systems and vibrations of their backbone...
Article
We report the isolation of hydroxy mercapto methylene (HO-C̈-SH) under cryogenic conditions via pyrolysis of 2-ethoxy-2-thioxo-acetic acid. The two most stable carbene rotamers form via extrusion of ethylene and CO2 from this precursor. This donor-stabilized carbene represents a hitherto uncharacterized CH2SO species and the first spectroscopically...
Article
We present an experimental and computational study of a cyclooctatetraene (COT)-based molecular balance disubstituted with commonly used silyl groups. Such groups often serve as protecting groups and are typically considered innocent bystanders. Our motivation here is to determine the actual steric effects of such groups by employing a molecular ba...
Article
The present personal perspective sheds light on the checkered history of hexaphenylethane (HPE) and some of its key derivatives, including successes and failures in interpreting experimental as well as computational data. HPE has become a testing ground for chemical theory since the groundbreaking work of Gomberg in 1900. It sparked the growth of t...
Chapter
Anion‐binding catalysis, which is characterized by a neutral or charged catalyst interacting with a negatively charged substrate, has emerged as a powerful method for stereoselective organocatalytic reactions. This chapter collects and emphasizes the structural design elements starting from nature's catalytic systems that can be transferred into sm...
Article
We present a new acid-free method for the generation of carbocations based on a redox condensation reaction that enables SN1 reactions with a variety of nucleophiles. We utilize readily synthesized phosphinites that are activated by diisopropyl azodicarboxylate to form betaine structures that collapse upon adding a pronucleophile, thereby yielding...
Article
We report the immobilization of 4‐dimethylaminopyridine (DMAP), a versatile organocatalyst for sterically demanding esterifications, on mesoporous SiO2 particles and self‐made macro‐mesoporous SiO2 monoliths, both possessing optimized properties for continuous flow catalysis. An alkyne‐functionalized DMAP derivative was immobilized via click chemis...
Article
We provide evidence for the first successful generation of phenylhydroxycarbene and 4-trifluoromethylphenylhydroxycarbene in solution. The carbene tautomers of the corresponding benzaldehyde derivatives had been prepared under cryogenic matrix-isolation conditions before but their reactivity, apart from a prototypical quantum mechanical tunneling [...
Article
We report the first preparation of N-alkoxyimidazolylidene (NOHC), a nucleophilic carbene based on an oxidized imidazolium core. The Arduengo-type analogous carbene center shows the most upfield 13C NMR shift compared to common NHCs. The obtained gold(I) complex of the carbene follows the 13C NMR upfield trend and shows the marked influence the alk...
Article
Full-text available
The first use of the bulky barrel-shaped ligand is demonstrated in HHUD-3, with accessible porosity only feasible for a defect structure. With 35%+ missing linker defects and SBET=890 m2g–1 (N2),...
Article
Full-text available
The search for methods to bind CO 2 and use it synthetically as a C 1 -building block under mild conditions is an ongoing endeavor of great urgency. The formation of heterocyclic carbene-carbon dioxide adducts...
Article
Full-text available
ZIP9 is a recently identified membrane-bound androgen receptor of physiological significance that may mediate certain physiological responses to androgens. Using in silico methods, six tetrapeptides with the best docking properties at the testosterone binding site of ZIP9 were synthesized and further investigated. All tetrapeptides displaced T-BSA-...
Article
New meta‐substituted tetraaryl adamantane derivatives were synthesized through one‐step Friedel‐Crafts adamantylation by using AlCl3 in combination with t‐butyl bromide. The products exhibit improved (over tetraphenyl adamantane) highly directional white‐light emission upon irradiation with a continuous wave (CW) laser diode. An easier path to orga...
Article
The Front Cover illustrates the conversion of red light from a continuous wave (CW) infrared laser into directed white light when passing through a sample of the inherently amorphous adamantane‐type cluster compound [(StySn)4S6] (sty=styryl). Cover design by Elisa Monte. More information can be found in the Minireview by Stefanie Dehnen, Peter R. S...
Article
The front cover artwork is provided by Stefanie Dehnen, Kerstin Volz, Wolf‐Christian Pilgrim (Philipps University Marburg), Peter R. Schreiner, Sangam Chatterjee, Doreen Mollenhauer, Simone Sanna (Justus Liebig University Giessen), and Nils W. Rosemann (Karlsruhe Institute of Technology). The image illustrates the conversion of red light from a con...
Article
We evaluate the use of the cohesive energy density (ced) as a quantitative descriptor for solvophobic effects in organic solvents by measuring ΔGZ/E of the rigid Z- and E-2,2'-diethynyl-9,9'-bifluorenylidene. In line with previously employed balances, solvent-dependent changes in ΔGZ/E are predominantly induced by solvophobic effects, leading to a...
Article
Full-text available
Polyhedral nitrogen containing molecules such as prismatic P3N3 - a hitherto elusive isovalent species of prismane (C6H6) - have attracted particular attention from the theoretical, physical, and synthetic chemistry communities. Here we report on the preparation of prismatic P3N3 [1,2,3-triaza-4,5,6-triphosphatetracyclo[2.2.0.02,6.03,5]hexane] by e...
Article
Novel nanocarbons such as fullerenes, nanotubes, graphene, and nanodiamond reside at the cutting edge of nanoscience and technology. Along with chemical functionalization, geometric constraints (such as extreme curvature in nanotubes or defects within or at the surfaces of diamond nanoparticles) significantly alter the electronic states of the nano...
Article
Chemie gebündelt in der GDCh.app
Article
Full-text available
Molecular compounds of the general formula [(RT) 4 E 6 ] (R = organic or organometallic substituent; T = C, Si, Ge, Sn; E = CH 2 , S, Se), hence adamantane derivatives and inorganic‐organic hybrid compounds based on a heteroadamantane structure, were shown to exhibit non‐linear optical response upon radiation with a continuous‐wave near‐infrared la...
Article
We generated and isolated hitherto unreported aminohydroxymethylene (1, aminohydroxycarbene) in solid Ar via pyrolysis of oxalic acid monoamide (2). Astrochemically relevant carbene 1 is persistent under cryogenic conditions and only decomposes to HNCO + H2 and NH3 + CO upon irradiation of the matrix at 254 nm. This photoreactivity is contrary to o...
Article
Full-text available
We present a computational analysis of hexaphenylethane derivatives with heavier tetrels comprising the central bond. In stark contrast to parent hexaphenylethane, the heavier tetrel derivatives can readily be prepared. In order to determine the origin of their apparent thermodynamic stability against dissociation as compared to the carbon case, we...
Article
The simplest α,β-unsaturated sulfinyl radical CH2[double bond, length as m-dash]C(H)SO˙ has been generated in the gas phase by high-vacuum flash pyrolysis (HVFP) of sulfoxide CH2[double bond, length as m-dash]C(H)S(O)CF3 at ca. 800 °C. Two planar cis and trans conformers of CH2[double bond, length as m-dash]C(H)SO˙ were isolated in cryogenic matrix...
Article
One year ago, Angewandte Chemie pledged to become a more inclusive and diverse journal. We have made significant progress, but our work is not done. Starting today with the inaugural ten Advisory Editors of the journal and our new Author Profiles “Introducing…”, and continuing over the next several months, we are pleased to share our achievements s...
Article
One year ago, Angewandte Chemie pledged to become a more inclusive and diverse journal. We have made significant progress, but our work is not done. Starting today with the inaugural ten Advisory Editors of the journal and our new Author Profiles “Introducing…”, and continuing over the next several months, we are pleased to share our achievements s...
Article
H-tunneling is a ubiquitous phenomenon, relevant to fields from biochemistry to materials science, but harnessing it for mastering the manipulation of chemical structures still remains nearly illusory. Here, we demonstrate how to switch on H-tunneling by conformational control using external radiation. This is outlined with a triplet 2-hydroxypheny...
Article
Halogens are rarely considered as dispersion energy donors for organic reaction design. Here, we re-examine one of the textbook examples for assessing steric hindrance, the A-value, and demonstrate that even in this system, halogens cannot be treated solely as classic repulsive hard spheres. A significant part of the steric demand of the halogens i...
Article
Full-text available
As low temperature conditions (e.g., in space) prohibit reactions requiring large activation energies, an alternative mechanism for follow‐up transformations of highly stable molecules involves the reactions of higher‐energy isomers that were generated in a different environment. Hence, one working model for the formation of larger organic molecule...
Article
Full-text available
The simple yet uncharacterized high energy tautomer of glycolic acid, namely 1,1,2-ethenetriol, an important molecule in the abiotic synthesis of sugar acids, has now been identified by IR and UV/Vis spectroscopy. With these data in hand, it now awaits its identification in space as another building block for prebiotic chemistry. Abstract As low-t...
Article
This themed collection contains a selection of articles on the topic of Understanding Dispersion Interactions in Molecular Chemistry.
Article
We present the first formation of the previously elusive phosphine imide (HN[double bond, length as m-dash]PH3) along with its phosphinous amide (H2N–PH2) isomer via exposure of phosphine (PH3) and ammonia (NH3) ices to ionizing radiation
Article
We report the on-surface chemistry of diamantanethiols on metal surfaces by combining low-temperature STM studies with quantum mechanical density functional theory computations. First, we examined the spatial configurations of diamantanethiols on metal surfaces, in which the thiol-substrate confinement plays a key role. We then thermally desorbed t...
Article
Full-text available
Head‐on Collision: Isolierte Triphenylmethan‐basierte Dimere in der Gasphase, die Dispersionsenergie‐Donoren enthalten, bilden eine Kopf‐an‐Kopf‐Struktur mit einem extrem kurzen C‐H⋅⋅⋅H‐C‐Abstand mit einer kollinearen Anordnung der Atome. Dieses überraschende Ergebnis aus Molekularstrahlexperimenten deutet darauf hin, dass London‐Dispersion und nic...
Article
The species on the C3H2O potential energy surface have long been known to play a vital role in extraterrestrial chemistry. Here we report on the hitherto uncharacterized isomer ethynylhydroxycarbene (H-C≡C-C̈-OH, 1) generated by high-vacuum flash pyrolysis of ethynylglyoxylic acid ethyl ester and trapped in solid argon matrices at 3 and 20 K. Upon...
Article
Full-text available
The triphenylmethane and all‐meta tert‐butyl triphenylmethane dimers, (TPM)2 and (TtBuPM)2, respectively, were studied with ionization loss stimulated Raman spectroscopy in molecular beam experiments to resolve structure sensitive vibrations. This answers the question whether the recently reported linear head‐to‐head arrangement in (TtBuPM)2 result...
Article
Herein, we report the oligopeptide-catalyzed site-selective acylation of partially protected monosaccharides. We identified catalysts that invert site-selectivity compared to N-methylimidazole, which was used to determine the intrinsic reactivity, for 4,6-O-protected glucopyranosides (trans-diols) as well as 4,6-O-protected mannopyranosides (cis-di...
Article
Fluorinated derivatives of biological molecules have proved to be highly efficient at modifying the biological activity of a given protein through changes in the stability and the kind of docking interactions. These interactions can be hindered or facilitated based on the hydrophilic/hydrophobic character of a particular protein region. Diadamantyl...
Article
Full-text available
As sulfur containing organic molecules thioamides and their isomers are conceivable intermediates in prebiotic chemistry, e. g. , in the formation of amino acids and thiazoles and resemble viable candidates for detection in interstellar media. Here we report the characterization of parent thioformamide in the solid state via single crystal X‐ray di...
Article
Wir gratulieren herzlich unseren Kolleginnen und Kollegen zu ihren Goldenen Jubiläen in der GDCh bzw. zu ihren 50‐jährigen Mitgliedschaften in der Chemischen Gesellschaft der DDR (CG) und nach der Wiedervereinigung in der GDCh:
Article
Metal–organic complexes with a pair of orthogonal π-systems lead to a new stacking motif in solid state and open the way to a new branch in the family of molecular semiconductors.
Article
Full-text available
Porous carrier materials functionalized with organocatalysts offer substantial advantages compared to homogeneous catalysts, e.g., easy separation of the catalyst, scalability, and an improved implementation in continuous operations. Here, we report the immobilization of (3-aminopropyl)trimethoxysilane (APTMS) onto self-prepared silica monoliths an...
Article
We present a comprehensive experimental study of a di-t-butyl-substituted cyclooctatetraene-based molecular balance to measure the effect of 16 different solvents on the equilibrium of folded versus unfolded isomers. In the folded 1,6-isomer, the two t-butyl groups are in close proximity (H···H distance ≈ 2.5 Å), but they are far apart in the unfol...
Article
We report the synthesis and absolute configuration of monodeuterated cis-perhydroazulene (d1-1), which is a rare example of an isotopically chiral hydrocarbon whose synthesis and stereochemical analysis are known to be particularly difficult. The synthesis features nickel-boride-catalyzed deuteration that allowed formation of the diastereomerically...
Article
Full-text available
Carbocations can be categorized into classical carbenium ions and non-classical carbonium ions. These intermediates are ubiquitous in reactions of both fundamental and practical relevance, finding application in the petroleum industry as well as the discovery of new drugs and materials. Conveying stereochemical information to carbocations is theref...
Article
We report the first preparation of the s-cis,s-cis conformer of dihydroxycarbene (1cc) by means of pyrolysis of oxalic acid, isolation of the lower-energy s-trans,s-trans (1tt) and s-cis,s-trans (1ct) product conformers at cryogenic temperatures in a N2 matrix, and subsequent narrow-band near-infrared (NIR) laser excitation to give 1cc. Carbene 1cc...
Article
Quantum mechanical tunneling is a consequence of the wave nature of particles that implies that a particle can penetrate a potential energy barrier even though there is insufficient energy to overcome it. This has serious consequences for chemical reactions, a fact that has, however, not been appreciated fully. Only in the last few years has it bec...
Article
Full-text available
The well‐known Corey‐Bakshi‐Shibata (CBS) reduction is a powerful method for the asymmetric synthesis of alcohols from prochiral ketones, often featuring high yields and excellent selectivi­ties. While steric repulsion has been regarded as the key director of the observed high enantioselectivity for many years, here we show that London dispersion (...
Article
Full-text available
London dispersion (LD) interactions facilitate the enantioselectivity in the Corey–Bakshi–Shibata (CBS) reduction. Employing a combination of computational and experimental studies, we provide a modern view on the origin of enantioselectivity in this powerful organocatalyzed reaction. The results demonstrate that attractive LD interactions between...
Article
Full-text available
Amide tautomers, which constitute the higher-energy amide bond linkage, not only are key for a variety of biological but also prebiotic processes. In this work, we present the gas-phase synthesis of 1-aminoethenol, the higher-energy tautomer of acetamide, that has not been spectroscopically identified to date. The title compound was prepared by fla...
Article
Pyruvic acid represents a key molecule in prebiotic chemistry to form metabolites and amino acids. Without liquid water on the early Earth, endogenous formation of pyruvic acid is unlikely, and an exogenous delivery constitutes an appealing alternative. However, despite the detection of more than 200 molecules in space, pyruvic acid is elusive. Her...
Article
Ein kontroverser Beitrag in der Angewandten Chemie und seine Folgen.
Article
Platinum-based antineoplastic agents play a major role in the treatment of numerous types of cancer. A new bulky, lipophilic, and chiral ligand based on 1,2-diaminodiamantane in both of its enantiomeric forms was employed for the preparation of new platinum(II) complexes with chloride and oxalate ligands. The dichloride complexes have a higher solu...
Article
Full-text available
We report on using the synthetic aminoadamantane-CH2-aryl derivatives 1-6 as sensitive probes for blocking M2 S31N and M2 WT channels as well as virus replication in cell culture. The binding kinetics for M2 S31N channel are very dependent on the length between the adamantane moiety and the first ring of the aryl head group realized in 2 and 3, and...
Article
Full-text available
Main-group-element compounds with energetically high-lying donor and low-lying acceptor orbitals are able to mimic chemical bonding motifs and reactivity patterns known in transition metal chemistry, including small-molecule activation and catalytic reactions. Monovalent group 13 compounds and divalent group 14 compounds, particularly silylenes, ha...
Article
Full-text available
Although the chemistry of phosphorus and nitrogen has fascinated chemists for more than 350 years, the Hückel aromatic cyclotriphosphazene (P 3 N 3 , 2 ) molecule—a key molecular building block in phosphorus chemistry—has remained elusive. Here, we report a facile, versatile pathway producing cyclotriphosphazene and its Dewar benzene–type isomer (P...
Article
On June 4, 2020, an Essay entitled “Organic synthesis–Where now?” is thirty years old. A reflection on the current state of affairs was published on the website of Angewandte Chemie as an “Accepted Article”. The article should have never been published, and we join the editors of Angewandte Chemie in sincerely apologizing for the offensive and misg...
Article
On June 4, 2020, an Essay entitled „Organic synthesis–Where now?“ is thirty years old. A reflection on the current state of affairs was published on the website of Angewandte Chemie as an „Accepted Article“. The article should have never been published, and we join the editors of Angewandte Chemie in sincerely apologizing for the offensive and misg...