02241nas a2200217   4500008004100000022001400041245015800055210006900213260000800282300001400290490000700304520143800311100001701749700002101766700003001787700002801817700001701845700001601862700001801878856012701896       2025                        eng d  a2041-652000aPhosphite mediated molecular editing via switch to meta-C-H alkylation of isoquinolines: emergence of a distinct photochemical [1,3] N to C rearrangement0 aPhosphite mediated molecular editing via switch to metaCH alkyla  cJAN  a1809-18180 v163 a<p>
	The isoquinoline core is present in one of the largest subsets of bioactive natural products. The multifunctional isoquinoline core exerts diverse bioactivity, resulting in the development of numerous isoquinoline-based drugs and molecules that are currently under clinical trials. We developed a new approach for phosphite-mediated [1,2] alkyl migration for an overall ortho-C-H alkylation via N-alkylation of isoquinoline. Tuning the phosphite-mediated protocol to switch the site selectivity would expedite direct and diverse multi-C-H bond functionalization. We report a new approach starting with a simple N-alkylation of isoquinoline with sterically and electronically diverse alkyl bromides for their phosphite-mediated photochemical [1,3] N to C rearrangement followed by a rearomatization sequence that leads to meta-C-H (C4) alkylation. Combined experimental and computational studies unveiled the emergence of an unprecedented C-N bond cleavage pathway from the singlet excited state of the enamine-type intermediate. Our radical bond-cleavage pathway favors substituted alkyl group migration that complements the recently successful meta-alkylation methods with smaller and more reactive electrophiles. This switch in site selectivity via tuning the phosphite-mediated protocol resulted in sequential C-H difunctionalization of isoquinoline including regiodivergent ortho, meta-dialkylations of isoquinolines.</p>
1 aRani, Soniya1 aRay, Anuj, Kumar1 aDewangan, Devendra, Kumar1 aPatil, Nita, Aruna Ramc1 aAarthika, M.1 aPaul, Ankan1 aMaity, Pradip  uhttps://library.ncl.res.in/content/phosphite-mediated-molecular-editing-switch-meta-c-h-alkylation-isoquinolines-emergence01560nas a2200253   4500008004100000022001400041245015100055210006900206260000900275300001400284490000700298520067500305100001800980700001700998700002801015700001901043700001901062700001601081700001801097700002401115700001701139700001801156856013201174       2025                        eng d  a1523-706000aUnified photoredox-catalyzed aerobic oxidative dynamic kinetic asymmetric transformation for C-N atropoisomers mediated by chiral organophosphites0 aUnified photoredoxcatalyzed aerobic oxidative dynamic kinetic as  cAUG   a8171-81770 v273 a<p>
	The synthesis of anilides with a chiral C(=O)-N axis has relied on direct installation of the chiral C(sp2)-N(sp2) bond or enantioselective modification of the peripheral groups. However, these methods are constrained by the size and type of functional groups compatible with each strategy. Herein, we report a dynamic kinetic asymmetric transformation (DYKAT) for the aerobic oxidation of iminium ions to access C(=O)-N axial chirality that addresses those limitations. Furthermore, it eliminates the need for any auxiliary functional groups, which enables us to develop a unified method for the synthesis of atroposelective isoquinolone, lactam, and amide.</p>
1 aSaikia, Pinku1 aAarthika, M.1 aBhattacharjya, Ayantika1 aMaity, Susmita1 aBajpai, Priyam1 aBera, Asish1 aSaha, Arindam1 aGonnade, Rajesh, G.1 aVanka, Kumar1 aMaity, Pradip  uhttps://library.ncl.res.in/content/unified-photoredox-catalyzed-aerobic-oxidative-dynamic-kinetic-asymmetric-transformation-c-n