Themed collection 2015 Emerging Investigators by OCF

Organic Chemistry Frontiers profiles the contributors to the “Emerging Investigators” themed collection.

This highlight presents advances in transition metal-catalysed alkene and alkyne hydroacylation over the past three years.

Recent emergence of photoredox/nickel dual catalysis to generate carbon–carbon and carbon–heteroatom bonds is highlighted.

Fluorinated solvents like 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) and trifluoroethanol (TFE) have recently emerged as a remarkable synthetic hint allowing challenging C–H activation reactions.

In this highlight, the design of cooperative non-covalent organocatalysis for the development of novel asymmetric oxidative C–H bond functionalization reactions is presented.

This review summarizes 50 years of attempts to observe, and finally isolate, the elusive oxyallyl derivatives.

Bis(stannylation) of propiolates with hexabutylditin is achieved under mild conditions using a cationic gold(I) catalyst.

A series of novel chiral monophosphine ligands Xiang-Phoses were designed and have been applied to the enantioselective gold-catalyzed intermolecular [2 + 2]-cycloaddition of 3-styrylindoles 1 with N-allenyl oxazolidinone 2.

A mild C–H allylation promoted by a cobalt salt combined with a Grignard reagent is described.

The t-BuOK-mediated reactions of γ,δ-alkenyl hydrazones enabled intramolecular hydroamination with the outer nitrogen, affording tetrahydropyridazine derivatives.

Various interesting nanostructures such as flowers and tadpole shaped structures were successfully obtained from well-defined cholesteryl-containing rhomboidal metallacycles prepared by coordination-driven self-assembly.

A novel method for the preparation of diverse allylic boronates from simple allylic alcohols is reported.

A new protocol for Pd-catalyzed β methylene C–H arylation of N-quinolyl cycloalkylcarboxamides with aryl iodides at room temperature is reported.

Ruthenium-catalyzed selective imine synthesis from nitriles and secondary alcohols under hydrogen acceptor- and base-free conditions was achieved.

An efficient palladium-catalyzed phosphonyldifluoromethylation of alkenes with bromodifluoromethylphosophonate is described. The method provides a facile access to a series of phosphonyldifluoromethylated alkenes that are of interest in medicinal chemistry. Mechanistic studies reveal that a phosphonyl difluouromethyl radical is involved in the reaction.

Co-catalyzed sequential hydroborations of alkyl and aryl alkynes with pinacolborane produce 1,1-diboronate esters with high selectivity and yields.

A simple and efficient visible-light promoted intermolecular haloamination and haloetherification of alkenes was reported.

A Pd(II)-catalyzed selective β-arylation of O-methyl ketoximes was developed using iodoarenes as the coupling partners.

A metal-free, photo-induced C–C bond formation methodology was developed to construct tetrahydrofluorenones and their related structures.

A ten-step (the longest linear sequence) total synthesis of sespenine was accomplished.

A novel iodine(III)-mediated synthesis of substituted phenanthrenes from ortho-vinylated biaryl derivatives through 6-endo-trig selective oxidative intramolecular arene–alkene coupling is reported.

The novel NHC-catalyzed dehydrogenative coupling of enals is described to generate a wide range of monobactams.

The Au-catalyzed tandem reaction provided simple and efficient access to spiro-dipyrroloquinolines and incargranine B aglycone and (±)-seneciobipyrrolidine (I).

Dearomative cycloadditions of imino esters derived from alanine with 3-nitroindoles form exo′-pyrroloindolines in good yields with high diastereo- and enantioselectivities.

A palladium/norbornene-catalyzed ortho-C–H alkylation and ipso-alkynylation reaction for the synthesis of 2-alkyl-1-alkynyl arenes was reported, where the use of bulky 1,1-dimethyl-2-alkynols led to significant suppression of the formation of O-alkylation and norbornene alkynylation by-products.

The synthesis of strained paracyclophanes is facilitated by ortho-substitution effect on phenyl ring.

A novel zinc based binary catalytic system for the synthesis of cyclic carbonates under mild and solvent-free conditions utilizing CO₂ as a C1 building block is reported.

A rhenium and base co-catalyzed [3 + 2] carbocyclization of N–H ketimines and alkynes through C–H bond activation is developed.

Palladium-catalysed cross-coupling of aminals with N-sulfonyl hydrazones has been established via C–N bond activation under base-free conditions.

Herein, we report our synthetic endeavors towards the synthesis of the C3–C14 fragment of the complex natural product alchivemycin A.

New glycosyl donors with recyclable and regenerable leaving groups, which could be activated via remote mode, were designed for latent-active glycosylation.

Isoxazoline-featured oxindoles were synthesized by the reaction of β,γ-unsaturated ketoximes with N-arylacrylamides via iminoxyl radical-promoted cascade intra/intermolecular oxyalkylation/alkylarylation of alkenes.

An efficient method for the preparation of aryl esters has been developed via Pd-catalyzed decarboxylative coupling of potassium aryltrifluoroborates and potassium oxalate monoesters.

Copper-catalyzed aminotrifluoromethylation of alkenes has been achieved using amides as nucleophiles to provide valuable CF₃-containing lactams in good yields under mild conditions.

A palladium-catalyzed oxidative arylation of lactic acid is described.

Synthesis of the 1,2,4-thiadiazole alkaloids polycarpathiamines A and B is described. The heteroaromatic core of the natural products was assembled using a one-pot benzylic oxidation–oxidative heterocyclization process.

The transition-metal-free aryne multicomponent coupling (MCC) involving carboxylic acids initiated by aziridines/azetidines leading to the synthesis of N-aryl β/γ-amino alcohol derivatives has been developed.

We demonstrated a systematic study of calixarene-induced aggregation (CIA) that how and to what extent the structures of hosts and guests affect the assembly behavior by fluorescence spectroscopy.

An efficient method for the direct C–H olefination of sulfocoumarins with a wide range of alkenes is developed. Moreover, O₂ was successfully utilized as the sole oxidant for the oxidative Heck reaction. This approach enables the rapid generation of various 3-alkenylated sulfocoumarins.

By changing the linkage position and linked number of the methyl group, the resultant AIE luminogens demonstrated adjustable intramolecular conjugation.

1,3,5-Substituted pyrrolidin-2-ones were synthesised via an iodine mediated cyclisation of 3-methyl substituted homoallylamines in good to excellent yield, as mixtures of diastereoisomers. Furan bispyrrolidines were formed as single diastereoisomers when 3-phenyl homoallylamines were employed in an analogous reaction.

A palladium-catalyzed C(sp³)–H arylation of adamantane at the methylene position with the assistance of an amide group was developed.