Annulative π-Extension (APEX): Rapid Access to Fused Arenes, Heteroarenes, and Nanographenes

Angewandte Chemie International Edition, Journal Year: 2017, Volume and Issue: 56(37), P. 11144 - 11164

Published: March 30, 2017

The annulative π-extension (APEX) reaction has the potential to have a tremendous impact on fields of materials science and bioimaging, as well pharmaceutical/agrochemical industries, since it allows access fused aromatic systems from relatively simple compounds in single step. Typically, an APEX facilitates one-pot without need prefunctionalize compounds. This advantageous feature is extremely useful for tuning modifying molecular properties last step synthesis. In this Review, progress applications reactions unfunctionalized arenes heteroarenes are described.

Language: Английский

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Direct (Hetero)arylation Polymerization: Trends and Perspectives

Journal of the American Chemical Society, Journal Year: 2016, Volume and Issue: 138(32), P. 10056 - 10071

Published: July 27, 2016

Conjugated polymers have attracted much attention in recent years, as they can combine the best features of metals or inorganic semiconducting materials (excellent electrical and optical properties) with those synthetic (mechanical flexibility, simple processing, low-cost production), thereby creating altogether new scientific synergies technological opportunities. In search for more efficient methods preparation conjugated polymers, this Perspective reports advances field direct (hetero)arylation polymerization. This recently developed polymerization method encompasses formation carbon–carbon bonds between (hetero)arenes (hetero)aryl halides, reducing both number steps production organometallic byproducts. Along these lines, we describe most general adaptable reaction conditions high-molecular-weight, defect-free polymers. We also discuss bottleneck presented by utilization certain brominated thiophene units propose some potential solutions. It is, however, firmly believed that will become a versatile tool providing desirable atom-economical alternative to standard cross-coupling reactions.

Language: Английский

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Ring Construction by Palladium(0)-Catalyzed C(sp³)–H Activation

Accounts of Chemical Research, Journal Year: 2017, Volume and Issue: 50(4), P. 1114 - 1123

Published: April 4, 2017

ConspectusThe catalytic activation and functionalization of unactivated C(sp3)–H bonds alkyl groups has undergone intense development in recent years. In particular, a variety directing as well native functional have been employed combination with palladium(II) catalysis order to perform intermolecular, some extent intramolecular reactions. parallel, inspired by precedents C(sp2)–H arylation, our group others developed different approach, which is the focus this Account. This strategy relies on use oxidative addition carbon-leaving bond palladium(0) induce subsequent formation C(sp2)–C(sp3) or C(sp3)–C(sp3) bond. Since first publication 2003, construction olefins and, more interestingly, an array valuable monocyclic polycyclic systems reported according principle. (Hetero)aryl bromides were initially reactants, but scope was later expanded include (hetero)aryl chlorides triflates, alkenyl bromides, carbamoyl α-chloroamides. Mechanistic studies enabled better understanding C–H step, proposed occur through ambiphilic metal–ligand activation-6 (AMLA-6), also known concerted metalation deprotonation (CMD), rationalization observed selectivity patterns. Moreover, wealth accumulated experimental data indicate that number atoms separating from Pd type are main factors controlling site-selectivity cleavage. Recent efforts devoted enantioselective To purpose, two strategies employed: chiral ancillary ligand achiral base, base ligand, allowed for achievement high enantioselectivities both tri- tetrasubstituted stereocenters. On other hand, current activation-based ring-forming method applied synthesis pharmacologically active substances agrochemicals, complex natural products such aeruginosins, thereby demonstrating its great potential step-economical organic synthesis.

Language: Английский

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Rhodium(III)‐Catalyzed Enantiotopic C−H Activation Enables Access to P‐Chiral Cyclic Phosphinamides

Angewandte Chemie International Edition, Journal Year: 2016, Volume and Issue: 56(1), P. 364 - 367

Published: Aug. 30, 2016

Abstract Compounds with stereogenic phosphorus atoms are frequently used as ligands for transition‐metal well organocatalysts. A direct catalytic enantioselective method the synthesis of P ‐chiral compounds from easily accessible diaryl phosphinamides is presented. The use rhodium(III) complexes equipped a suitable atropochiral cyclopentadienyl ligand shown to enable an enantiodetermining C−H activation step. Upon trapping alkynes, broad variety cyclic phosphorus(V) atom formed in high yields and enantioselectivities. Moreover, these can be reduced enantiospecifically phosphorus(III) compounds.

Language: Английский

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A Perspective on Late-Stage Aromatic C–H Bond Functionalization

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(6), P. 2399 - 2414

Published: Jan. 27, 2022

Late-stage functionalization of C-H bonds (C-H LSF) can provide a straightforward approach to the efficient synthesis functionalized complex molecules. However, LSF is challenging because bond must be in presence various other functional groups. In this Perspective, we evaluate aromatic on basis four criteria─reactivity, chemoselectivity, site-selectivity, and substrate scope─and our own views current challenges as well promising strategies areas growth going forward.

Language: Английский

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