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The inertness of chloroalkanes has precluded them as coupling partners for cross‐coupling reactions. Herein we disclose a general strategy for the activation of inert alkyl chlorides through photoredox catalysis and their use as coupling partners with alkenes. The catalytic system is formed by [Ni(OTf)(Py2Tstacn)](OTf) (1Ni), which is responsible for the Csp3−Cl bond activation, and [Ir(NMe2bpy)(ppy)2]PF6, (PCIrNMe2), which is the photoredox catalyst. Combined experimental and theoretical studies show an in situ photogenerated NiI intermediate ([Ni(Py2Tstacn)]+) which is catalytically competent for the Csp3−Cl bond cleavage via a SN2 mechanism for primary alkyl chlorides, forming carbon‐centered free radicals, which react with the olefin leading to the formation of the Csp3−Csp3 bond. These results suggest inert alkyl chlorides can be electrophiles for developing new intermolecular strategies in which low‐valent aminopyridine nickel complexes act as key catalytic species. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: The asymmetric reductive arylation and alkenylation of benzylic chloride under photoredox/nickel dual catalysis using chiral biimidazoline (BiIm) ligand is reported to access 1,1‐diaryl alkanes and aryl allylic compounds with good yield as well as stereo‐ and enantioselectivities. This protocol uses more commercially available and less expensive C(sp2)‐Br as the electrophile coupling partner. A primary result using alkenyl chloride and alkyl chloride is also reported. Various functional groups are tolerated and the applications of this method are investigated by late‐stage functionalization and gram‐scale reaction. [ABSTRACT FROM AUTHOR]

A protocol for performing atom transfer radical addition of activated alkyl chlorides to alkenes is described. The reaction is promoted by blue light in the presence of an organic photocatalyst (3DPA2FBN), serving to generate free radicals, and a copper complex (IMesCuCl), which facilitates the chlorine transfer step. The reaction works efficiently with fluorinated and non‐fluorinated α‐chloroesters. [ABSTRACT FROM AUTHOR]

A method for the synthesis of water-soluble α-aminopyrroles, 1-(2-amino-1H-pyrrol-3-yl)pyridinium chlorides, by the reaction 1-(cyanomethyl)pyridinium chloride with alkyl 3-aryl-2H-azirine-2-carboxylates was developed. [ABSTRACT FROM AUTHOR]

New bispyridinium dichlorides based on 2,2-bis(hydroxymethyl)propane-1,3-diyl spacer were synthesized from pentaerythritol, 4-aminopyridine, and carboxylic acids. The resulting biocides possess a high antibacterial effect. The minimal inhibitory concentration (MIC) of these compounds against pathogenic bacteria, namely, gram-positive Methicillin-resistant Staphylococcus aureus (strain ATCC 25923) and gram-negative Escherichia coli (ATCC 25922) and Pseudomonas aeruginosa (ATCC 27853), was established. The influence of the alkyl substituent length in salts on their microbiological activity was studied. [ABSTRACT FROM AUTHOR]

NMP-mediated chlorination of aliphatic alcohols has been developed for the synthesis of alkyl chlorides. This facile, efficient and practical approach used simple and readily available aryl sulfonyl chlorides as the chlorination reagent for the construction of C-Cl bond in good to excellent yields with mild conditions and broad substrate scope. [ABSTRACT FROM AUTHOR]

A direct nucleophilic trifluoromethylthiolation of alkyl chlorides, bromides and tosylates with AgSCF3 was described. It was found that the presence of nBu4NI or a combination of nBu4NI/ nBu4NBr significantly enhanced the reaction rates. The reaction conditions were mild, thus allowing the tolerance of a variety of functional groups. [ABSTRACT FROM AUTHOR]

A series of N-alkyl- N, N-dimethyl- N-( o-hydroxymethyl)benzylammonium chlorides surfactants (DHBA- m) were synthesized using o-chloromethylbenzyl alcohol and N-alkyl- N, N-dimethyl tertiary amine as raw materials. The structure of the products was confirmed by FT-IR, H NMR, C NMR and MS. DHBA- m surfactants exhibit low Krafft points and high surface activities. The process of micellization of DHBA- m is spontaneous, exothermic, and entropy-driven. The hydroxymethyl substitution increases hydrophobicity of DHBA- m, thus making micellization more favorable compared with that of N-dodecyl- N, N-dimethyl- N-benzylammonium chlorides (DDBAC- m). The bactericidal activity of DHBA- m is stronger on E. coli than that of DDBAC-12, and DHBA-16 shows strong bactericidal activity on Salmonella, S. aureus, and Streptococcus. [ABSTRACT FROM AUTHOR]

A batchwise, multigram preparation of 2-azabicyclo- [2.1.1]hexane hydrochloride (1·HCl) was developed, delivering a total of 195 grams of material. The key synthetic step involves an intramolecular displacement of a primary alkyl chloride with a tert-butylsulfinamide to forge the [2.1.1]-bicyclic ring system. [ABSTRACT FROM AUTHOR]

Trichloroisocyanuric acid with triphenylphosphine in anhydrous acetonitrile will convert alcohols into alkyl halides. [ABSTRACT FROM AUTHOR]

The front cover image, provided by Torben Rogge, Ruhuai Mei and Lutz Ackermann, illustrates the synthetic utility of cobalt ‐ catalyzed C – H arylations by oxazoline assistance at ambient temperature. The catalytic system derived from inexpensive Co(acac)2 and an N ‐ heterocyclic carbene enabled C – H arylations with ample scope, and proved applicable to difficult C – H alkylations with unactivated primary and secondary alkyl chlorides. The power of the C – H arylation strategy was reflected by C – H activation at 23 °C, and late ‐ stage diversification to access bioactive biaryls. Details can be found in the full paper on pages 2443 – 2448 (R. Mei, L. Ackermann, Adv. Synth. Catal. 2016, 358, 2443 – 2448; DOI: 10.1002/adsc.201600384). [ABSTRACT FROM AUTHOR]