Although greener and faster access to fine chemicals and APIs is highly desirable, there are currently no synthetic methodologies which undergo reaction completions within a few seconds to minutes in water under benchtop laboratory conditions. Here, we report a methodology that allows the instantaneous formation of ligated ultrasmall Pd nanoparticles in the hydrophobic pockets of benign cellulose derivative (HPMC) for chemical reactions to proceed very fast in water under mild reaction conditions. Unprecedented short reaction times were exemplified for the Buchwald–Hartwig aminations. In addition, very short reaction times of less than a minute were also demonstrated for the amide couplings, which is the most utilized reaction type in the pharmaceutical industry.

Hydrazines form a new family of low molecular-weight reducing agents for diazonium salts. Using only small amounts of hydrazine catalyst, the coupling of diazonium salts to a variety of reactive partners has been achieved, without the requirement for either metal adjuvants or irradiation with visible or ultraviolet light. The generality of the concept proposed herein as well as its advantages in the preparative scale is outlined and discussed.

Last‐minute deal: A direct lactonisation of ethers and alcohols onto amides that proceeds at room temperature under mild conditions is reported (see scheme). This allows the effective saving of up to two unproductive, sequential deprotection operations in synthetic sequences. Mechanistic studies are described, and a new “amide strategy” that exploits the dual robustness/late‐stage selective activation properties of this functional group is outlined.

We report a novel approach to the classical natural product quinine that is based on two stereoselective key steps, namely a C−H activation and an aldol reaction, to unite the two heterocyclic moieties of the target molecule. This straightforward and flexible strategy enables a concise synthesis of natural (−)‐quinine, the first synthesis of unnatural (+)‐quinine, and also provides access to unprecedented C3‐aryl analogues, which were prepared in only six steps. We additionally demonstrate that these structural analogues exhibit improved antimalarial activity compared with (−)‐quinine both in vitro and in mice infected with Plasmodium berghei.

In order to examine the influence of the alkyl chain length on some physical properties of guanidinium salts, the synthesis of a homologous series of new N″-n-alkylsubstituted N,N-diethyl-N′ ,N′- di-n-propyl-N″-n-hexyl guanidinium ionic liquids (gILs), containing chloride (Cl), tetrafluoroborate (BF4), acesulfamate (Ace), saccharinate (Sac), and tosylate (Tos) as anions, is reported. Cn-gILAce, Cn-gILSac, and Cn-gILBF4 were obtained by ion exchange reaction of the corresponding hexasubstituted guanidinium chlorides (Cn-gCl, n = 3, 4, 6, 8, 10), which were synthesized by a quaternization reaction of the pentaalkyl-substituted guanidine 3 and the corresponding alkylchloride in DMF. The tosylates gILs Cn-gTos (n = 1, 2, 4, 6, 8, 10) were synthesized by alkylation of 3 with the corresponding alkyltosylates. Some physical properties, such as solubility in water and organic solvents, refractive index and density, are considered as a function of the length of the n-alkyl substituent R and the nature of the anion

The Suzuki-Miyaura coupling reaction of electron-poor aryl chlorides in the synthesis of crop protection-relevant active ingredients in water is disclosed. Optimisation of the reaction conditions allowed to run the reaction...

No abstract

Anilides are often found in pharmaceuticals and active ingredients in crop protection. Although of great interest, the atom‐ and step economic formation of the amide bond between a less nucleophilic aniline with an acid or ester remains still a major challenge. Herein, we report an aminolysis of aromatic and alkyl esters with anilines catalyzed by a readily available catalytic system comprising of an earth‐abundant Mn‐salt in combination with an inexpensive base.