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Directing group assisted rhodium catalyzed meta-C–H alkynylation of arenes† † Electronic supplementary information (ESI) available. See https://doi.org/10.1039/d2sc00982j

ABSTRACT: Site-selective C–H alkynylation of arenes to produce aryl alkynes is a highly desirable transformation due to the prevalence of aryl alkynes in various natural products, drug molecules and in materials. To ensure site-selective C–H functionalization, directing group (DG) assisted C–H activation has been evolved as a useful synthetic tool. In contrast to DG-assisted ortho-C–H activation, distal meta-C–H activation is highly challenging and has attracted significant attention in recent years. However, developments are majorly focused on Pd-based catalytic systems. In order to diversify the scope of distal meta-C–H functionalization, herein we disclosed the first Rh(i) catalyzed meta-C–H alkynylation protocol through the inverse Sonogashira coupling reaction. The protocol is compatible with various substrate classes which include phenylacetic acids, hydrocinnamic acids, 2-phenyl benzoic acids, 2-phenyl phenols, benzyl sulfonates and ether-based scaffolds. The post-synthetic modification of meta-alkynylated arenes is also demonstrated through DG-removal as well as functional group interconversion. An unprecedented report on Rh-catalyzed meta-C–H alkynylation of arenes, aided by a weakly coordinating cyano-based directing template, was developed using bromoalkynes as the coupling partner.

SUBMITTER: Sasmal S

PROVIDER: S-EPMC9116288 | biostudies-literature | 2022 Apr

REPOSITORIES: biostudies-literature

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Project description:The synthesis and bottom-up assembly of nanocellulose by microbes offers unique advantages to tune and meet key design criteria—rapid renewability, low toxicity, scalability, performance, and degradability—for multi-functional, circular economy textiles. However, development of green processing methods that meet these criteria remains a major research challenge. Here, we harness microbial biofabrication of nanocellulose and draw inspiration from ancient textile techniques to engineer sustainable biotextiles with a circular life cycle. The unique molecular self-organization of microbial nanocellulose (MC) combined with bio-phosphorylation with a lecithin treatment yields a compostable material with superior mechanical and flame-retardant properties. Specifically, treatment of MC with a lecithin-phosphocholine emulsion makes sites available to modulate cellulose cross-linking through hydroxyl, phosphate and methylene groups, increasing the interaction between cellulose chains. The resultant bioleather exhibits enhanced tensile strength and high ductility. Bio-phosphorylation with lecithin also redirects the combustion pathway from levoglucosan production towards the formation of foaming char as an insulating oxygen barrier, for outstanding flame retardance. Controlled color modulation is demonstrated with natural dyes. Life cycle impact assessment reveals that MC bioleather has up to an order of magnitude lower carbon footprint than conventional textiles, and a thousandfold reduction in the carcinogenic impact of leather production. Eliminating the use of hazardous substances, these high performance materials disrupt linear production models and strategically eliminate its toxicity and negative climate impacts, with widespread application in fashion, interiors and construction. Importantly, the biotextile approach developed in this study demonstrates the potential of biofabrication coupled with green chemistry for a circular materials economy. Harnessing microbial biofabrication coupled to a protocol inspired by indigenous textile processes, we engineer high-performance biotextiles with a sustainable circular life cycle, including the plant and mineral dyed bioleather sneakers shown.

Dataset Information

Directing group assisted rhodium catalyzed meta-C–H alkynylation of arenes† † Electronic supplementary information (ESI) available. See https://doi.org/10.1039/d2sc00982j

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