Peter Huy

Rostock University, Homepage: peterhuylab.de · Institute for Chemistry

Herein, the first organocatalytic method for the transformation of non‐derivatized formic acid into carbon monoxide (CO) is introduced. Formylpyrrolidine (FPyr) and trichlorotriazine (TCT), which is a cost‐efficient commodity chemical, enable this decarbonylation. Utilization of dimethylformamide (DMF) as solvent and catalyst even allows for a rapi...

Nucleophilic substitutions (SN) account for the most essential and frequently applied chemical transformations. SN‐reactions allow forging C–C, C–O, C–N and C–Cl bonds, for example, from natural abundant starting materials such as alcohols and carboxylic acids. Products of SN‐reactions are ubiquitous and find inter alia applications as pharmaceutic...

A novel, broadly applicable method for the amide C-N and ester C-O bond formation is presented based on formylpyrrolidine (FPyr) as Lewis base catalyst. Thereby, trichlorotriazine (TCT), which is the most cost-efficient reagent for OH-group activations, was employed in amounts of ≤40 mol% with respect to the starting material (100 mol%). The new ap...

A practical method for the nucleophilic substitution (SN) of alcohols furnishing alkyl chlorides, bromides, and iodides under stereochemical inversion in high catalytic efficacy is introduced. The fusion of diethylcyclopropenone as a simple Lewis base organocatalyst and benzoyl chloride as a reagent allows notable turnover numbers up to 100. Moreov...

A simple formamide catalyst facilitates the efficient transformation of alcohols into alkyl chlorides with benzoyl chloride as the sole reagent. These nucleophilic substitutions proceed through iminium-activated alcohols as intermediates. The novel method, which can be even performed under solvent-free conditions, is distinguished by an excellent f...

Unter anderem das hat die Organik im letzten Jahr bewegt: milde Oxidation mit Elektrochemie, Oxidation zu enantiomerenreinen Sulfonylverbindungen, Flüssigkristallphasen erkennen mit maschinellem Lernen, CO 2 reagiert zu Succinat und Carbamaten, eine Alternative zu Bisphenol A, Subporphyrine, photoschaltbare Spinmaterialien, photochemische Thiophen‐...

Polystyrolproben werden mit Eisen(III)chlorid und weißen LEDs zu Oligomeren und Benzoylprodukten; ein Wolframatkatalysator invertiert die Absolutkonfiguration an sp3‐Kohlenstoffzentren; gelöstes Rätsel um eine symmetrieverbotene konrotatorische 14‐Elektronen‐Elektrocyclisierung; Polycarbonate, die sich ohne Lösungsmittel recyceln lassen: Highlights...

Hybride Lehrformen kombinieren klassische Veranstaltungen mit der Online‐Übertragung von Lehrinhalten. Hybridlehre hat somit eine Schlüsselfunktion, um Studierenden wieder Unterricht in Präsenz zu ermöglichen. Die Umsetzung erfordert allerdings mehr technische Ausstattung, als in den meisten Hörsälen vorhanden ist. Ein Erfahrungsbericht.

The Cover Feature shows the Lewis base‐catalyzed activation of alcohols for nucleophilic substitutions (SN) using phenyl chloroformate (PCF) as inherently safe phosgene substitute. In their Full Paper, B. Zoller et al. explain that SN‐reactions are typically facilitated by stoichiometric reagents, which effect an enhanced thermodynamic driving forc...

Nucleophilic substitutions (SN) are typically promoted by acid chlorides as sacrificial reagents to improve the thermodynamic driving force and lower kinetic barriers. However, the cheapest acid chloride phosgene (COCl2) is a highly toxic gas. Against this background, phenyl chloroformate (PCF) was discovered as inherently safer phosgene substitute...

Radicals can be generated at room temperature by means of visible light, when certain catalysts are engaged. Conventional protocols are mainly limited to the formation of radicals that are stabilized by adjacent electron withdrawing groups. Novel methods also enable the formation of non-stabilized radicals from naturally abundant alcohols and amine...

Mit sichtbarem Licht lassen sich in Gegenwart bestimmter Katalysatoren Radikale bei Raumtemperatur erzeugen. Bisher waren diese Methoden auf Radikale begrenzt, die durch elektronenziehende Substituenten stabilisiert sind. Neuerdings sind auch nicht stabilisierte Radikale aus Alkoholen und Aminen zugänglich.

The Cover Feature shows Lewis base catalyzed nucleophilic substitutions (SN) engaging non‐activated alcohols, carboxylic acids, aldehydes, and epoxides as substrates. In fact, SN‐transformations are of fundamental significance in chemistry. Especially in the last decade, powerful catalytic approaches for SN‐type C–C, C–N, C–O, and C–Cl bond formati...

Certain micro algae produce so-called sulfolipids, a class of polychlorinated natural products. Consumption of these cell toxins by humans by means of mussels and shell fish can cause seafood poisoning. The rich stereochemistry and structural complexity of these natural products makes their synthesis challenging. Recent reports allow for an insight...

Einige Mikroalgen produzieren Sulfolipide, also polychlorierte Moleküle. Nehmen Menschen diese Zellgifte über Muscheln und Schalentiere auf, erkranken sie an Lebensmittelvergiftungen. Die Stereochemie dieser Verbindungen erschwert die Totalsynthesen von Vertretern dieser Naturstofffamilie. Aktuelle Arbeiten geben einen ersten Einblick in Wirkungswe...

This updatetoScience of SynthesisSection 32.4 compiles methods for the synthesis of chlo-ro-, bromo-, and iodoalkanes reported since 2007. Starting materials include alkenylmetalcompounds, alkenes, haloalkanes, carbonyl compounds, enoic acids, alkynes, haloalkynes, and allenes, among others. The advantages and limitations of the different ap-proach...

Boron-containing Lewis acids such as boronic acids, borates and boric acid allow for the direct dehydrative condensation of carboxylic acids with amines to afford amides. These catalysts not only enable the formation of peptide C-N bonds without epimerization, but also tolerate acid labile functional groups.

Herein, a novel method for the transformation of aldehydes into geminal dichlorides based on phthaloyl chloride as reagent and N-formylpyrrolidine as Lewis base catalyst is disclosed. Given the mild reaction conditions, the current protocol is distinguished by high levels of functional group compatibility and scalability and is operationally simple...

Borhaltige Lewis‐Säuren wie Boronsäuren, Borate oder Borsäure ermöglichen, Carbonsäuren und Amine direkt zu Amiden zu kondensieren. Mit diesen Reagenzien lassen sich nicht nur Peptidbindungen ohne Verlust an Stereoisomerenreinheit knüpfen, sondern die Reaktion funktioniert auch mit säureempfindlichen funktionellen Gruppen.

Herein, a method for the nucleophilic substitution (SN) of benzyl alcohols yielding chloro alkanes is introduced that relies on aromatic sulfoxides as Lewis base catalysts (down to 1.5 mol%) and benzoyl chloride (BzCl) as reagent. A systematic screening of various sulfoxides and other sulfinyl containing Lewis bases afforded methyl(2‐methoxyphenyl)...

Substitution reactions belong to the most fundamental transformations in chemistry. However, they are commonly restricted by a poor sustainability, as at least one waste byproduct is formed. Herein, a general and highly efficient formamide‐catalyzed method for nucleophilic substitution of alcohols furnishing alkyl chlorides is presented, in which t...

Herein, a general formamide catalyzed protocol for the efficient transformation of alcohols into alkyl chlorides, which is promoted by substoichiometric amounts (down to 34 mol%) of inexpensive trichlorotriazine (TCT), is introduced. Importantly, the present work is the first example of a TCT mediated dehydroxychlorination of an OH-group containing...

A simple formamide catalyst facilitates the efficient transformation of alcohols into alkyl chlorides with benzoyl chloride as the sole reagent.

Nucleophilic substitutions (SN) at sp³-hybridized carbon centers are one of the most fundamental type of transformation in organic synthesis. Taking the importance of bimolecular SN reactions into account, catalytic variants must be considered as underdeveloped. This review highlights the most recent progress in the emerging field of Lewis base cat...

Ein einfacher Formamidkatalysator ermöglicht effiziente Transformationen von Alkoholen zu Alkylchloriden mit Benzoylchlorid als einzigem Reagenz. Diese nukleophilen Substitutionsreaktionen verlaufen über iminiumaktivierte Alkohole als Intermediate. Die neue Methode, die sogar lösungsmittelfrei durchgeführt werden kann, zeichnet sich durch eine exze...

Significance Protein–protein interactions mediated by proline-rich motifs are involved in regulation of many important signaling cascades. Protein domains specialized in recognition of these motifs expose a flat and relatively rigid binding site that preferentially interacts with sequences adopting a left-handed polyproline helix II. Here, we prese...

A concise (5 to 6 steps), stereodivergent, highly diastereoselective (dr up to >19:1 for both stereoisomers) and scalable synthesis (up to 14 g) of cis- and trans-2-substituted 3-piperidinols, a core motif in numerous bioactive compounds, is presented. This sequence allowed an efficient synthesis of the NK-1 inhibitor L-733,060 in 8 steps. Addition...

A stereodivergent and highly diastereoselective (dr up to >19:1 for both isomers), step economic (5-6 steps), and scalable synthesis (up to 14 g) of cis- and trans-2-substituted 3-piperidinols, the core motif of numerous bioactive compounds, providing efficient access to the NK-1 inhibitor L-733,060 is presented. Additionally, a "traceless" (referr...

A practical and scalable synthesis of a Fmoc-protected tricyclic dipeptide mimetic (6), that is, a 1,4-diaza-tricyclo-[8.3.0(3,7)]-tridec-8-ene derivative resembling a rigidified di-L-proline in a polyproline type II (PPII) helix conformation, was developed. The strategy is based on a Ru-catalyzed ring-closing metathesis of a dipeptide (4) prepared...

Solubilization of proline as the triethylammonium salt allows N-protection (as the Boc, Cbz or Moc derivative) and subsequent esterification or amidation of the carboxy terminus to be performed in an efficient one-pot fashion. Based on this concept, highly practical protocols were developed to prepare a series of proline derivatives (including Pro-...

A practical four-step synthesis of 3-alkyl-, vinyl-, and aryl-substituted proline derivatives, which are important building blocks for conformationally restrained peptide analogs, was developed. The method relies on a Cu-catalyzed 1,4-addition of Grignard reagents to N-protected 2,3-dehydroproline esters, efficiently prepared in a new one-pot proto...

Das X markiert den Punkt, an dem die Aminosäure X (siehe Struktur; grau C, cyan H, blau N, rot O, gelb Doppelbindung) als Pro-Pro-Ersatz in zwei Peptide eingebaut werden konnte, die an die prolinreiche Motive erkennende Domäne Fyn-SH3 binden, ohne ihre Bindungsfähigkeit zu gefährden. Das Dipeptidanalogon X, das in einer Polyprolin-Typ-II-Helixkonfo...

X marks the spot: The synthetic tricyclic amino acid X (see structure; C gray, H cyan, N blue, O red, double bond yellow) can be incorporated, without loss of binding ability, as a Pro-Pro substitute into two peptides that bind to the proline-rich motif-recognizing domains Fyn-SH3. The dipeptide analogue X, which is locked in a polyproline type II...