Helicity-modulated remote C-H functionalization.

Remote C-H functionalization is highly important for the conversion and utilization of arenes, but the conventional routes are comprehensively developed with the assistance of transition metal catalysts or templates. We report a facile metal/template-free electrochemical strategy for remote C-H functionalization in a helical system, where aromatic or aliphatic hydrogen act as a directing group to promote the alkoxylation at the opposite site of the helical skeleton by generating a unique helical "back-biting" environment. Such helicity-modulated C-H functionalization is prevalent for carbo[n]helicenes (n = 6 to 9, primitive or substituted) and hetero[6]helicenes and also occurs when the aryl hydrogen on the first position is replaced by a methyl group or a phenyl group. Thus, the relatively inert helicene skeleton can be precisely furnished with a rich array of alkoxy pendants with tunable functional moieties. Notably, the selective decoration of a methoxy group on N-methylated aza[6]helicene close or distant to the nitrogen atom leads to distinct luminescence variation upon changing the solvents.

A high-quality genome assembly of Jasminum sambac provides insight into floral trait formation and Oleaceae genome evolution.

As one of the most economically significant Oleaceae family members, Jasminum sambac is renowned for its distinct sweet, heady fragrance. Using Illumina reads, Nanopore long reads, and HiC-sequencing, we efficiently assembled and annotated the J. sambac genome. The high-quality genome assembly consisted of a total of 507 Mb sequence (contig N50 = 17.6 Mb) with 13 pseudomolecules. A total of 21,143 protein-coding genes and 303 Mb repeat sequences were predicted. An ancient whole-genome triplication event at the base of Oleaceae (~66 million years ago [Ma], Late Cretaceous) was identified and this may have contributed to the diversification of the Oleaceae ancestor and its divergence from the Lamiales. Stress-related (e.g., WRKY) and flowering-related (e.g., MADS-box) genes were located in the triplicated regions, suggesting that the polyploidy event might have contributed adaptive potential. Genes related to terpenoid biosynthesis, for example, FTA and TPS, were observed to be duplicated to a great extent in the J. sambac genome, perhaps explaining the strong fragrance of the flowers. Copy number changes in distinct phylogenetic clades of the MADS-box family were observed in J. sambac genome, for example, AGL6- and Mα- were lost and SOC- expanded, features that might underlie the long flowering period of J. sambac. The structural genes implicated in anthocyanin biosynthesis were depleted and this may explain the absence of vivid colours in jasmine. Collectively, assembling the J. sambac genome provides new insights into the genome evolution of the Oleaceae family and provides mechanistic insights into floral properties.

Transformation of Crowded Oligoarylene into Perylene-Cored Chiral Nanographene by Sequential Oxidative Cyclization and 1,2-Phenyl Migration.

Synthetic innovation for constructing sophisticated nanographenes is of fundamental significance for a variety of advanced applications. Herein, we report a distinctive method to prepare π-extended chiral nanographenes with 29 benzenoid rings and two helical breaches from a highly crowded perylene-cored oligoarylene precursor. Under Scholl's conditions, the reaction predominantly involves the regioselective and sequential cyclization in the peri- and bay regions of the perylene core, and the complanation of the 1-phenyl[5]helicene intermediate module via 1,2-phenyl migration. The resulting chiral nanographenes are configurationally stable at 180 °C due to the high diastereomerization barriers of ca. 45 kcal mol-1 . These molecules also possess globally delocalized π-systems with low HOMO/LUMO gaps, leading to nearly panchromatic absorption, intensive electronic circular dichroism signals and deep-red circularly polarized luminescence.

Oxidative cyclo-rearrangement of helicenes into chiral nanographenes.

Nanographenes are emerging as a distinctive class of functional materials for electronic and optical devices. It is of remarkable significance to enrich the precise synthetic chemistry for these molecules. Herein, we develop a facile strategy to recompose helicenes into chiral nanographenes through a unique oxidative cyclo-rearrangement reaction. Helicenes with 7~9 ortho-fused aromatic rings are firstly oxidized and cyclized, and subsequently rearranged into nanographenes with an unsymmetrical helicoid shape through sequential 1,2-migrations. Such skeletal reconstruction is virtually driven by the gradual release of the strain of the highly distorted helicene skeleton. Importantly, the chirality of the helicene precursor can be integrally inherited by the resulting nanographene. Thus, a series of chiral nanographenes are prepared from a variety of carbohelicenes and heterohelicenes. Moreover, such cyclo-rearrangement reaction can be sequentially or simultaneously associated with conventional oxidative cyclization reactions to ulteriorly enrich the geometry diversity of nanographenes, aiming at innovative properties.