01750nas a2200229 4500008004100000022001400041245009200055210006900147260000800216300001500224490000600239520100200245653001501247653001401262653001601276653001101292653002601303100002401329700001901353700002801372856012001400 2024 eng d a2365-654900aStrategies employing transition-metal free conditions for C-C bond formation in indoles0 aStrategies employing transitionmetal free conditions for CC bond cSEP ae2024032800 v93 a

Indole motifs are omnipresent in nature and can be found in many natural products as well as pharmaceuticals. It is for this reason synthetic transformations of indole have become a topic of interest for the organic and medicinal chemist community for decades. In this review, we have emphasized the functionalization of indoles via transition-metal-free approaches. This review touches on many aspects in different sub-sections, which gives a proposition of the tactics employed for the functionalization of indoles and an overview of the road ahead. In this review, essentially transition-metal-free conditions for C-C bond formation reactions in indoles has been explored. This review describes various approaches of functionalization at the C-2, C-3, C-4 and C-7 position of indoles which comprises arylation, alkenylation, acylation, formylation, alkylation, bisindolyl and cyclization strategies. Also, strategies incorporating N-alkylation/arylation has also been covered. image

10aAlkylation10aArylation10aformylation10aIndole10atransition-metal free1 aGhodake, Balaji, M.1 aPaul, Sayantan1 aBhattacharya, Asish, K. uhttps://library.ncl.res.in/content/strategies-employing-transition-metal-free-conditions-c-c-bond-formation-indoles01201nas a2200181 4500008004100000022001400041245014200055210006900197260000800266300001400274490000700288520050100295100002100796700002400817700002400841700002800865856012600893 2025 eng d a1477-052000aCatalyst and transition-metal free 1,6-conjugate addition of azobisisobutyronitrile: access to isobutyronitrile containing diarylmethanes0 aCatalyst and transitionmetal free 16conjugate addition of azobis cAPR a3956-39660 v233 a

A catalyst and transition-metal free 1,6-conjugate addition of azobisisobutyronitrile to para-quinone methides for the synthesis of isobutyronitrile containing diarylmethanes has been achieved. This protocol enables the synthesis of isobutyronitrile containing diarylmethanes in good yields and with a broad substrate scope. This is the first example wherein azobisisobutyronitrile has been used as a cyanide source for 1,6-conjugate addition under catalyst and metal-free conditions.

1 aMamale, Ajay, G.1 aGhodake, Balaji, M.1 aGonnade, Rajesh, G.1 aBhattacharya, Asish, K. uhttps://library.ncl.res.in/content/catalyst-and-transition-metal-free-16-conjugate-addition-azobisisobutyronitrile-access01424nas a2200157 4500008004100000022001400041245011700055210006900172260000800241300001400249490000700263520081700270100002401087700002801111856012701139 2026 eng d a1477-052000aOne-pot synthesis of N-arylated benzotriazoles and benzotriazinones via in situ diazotization and aryne trapping0 aOnepot synthesis of Narylated benzotriazoles and benzotriazinone cJUN a4696-47110 v243 a

N-Arylated benzotriazoles and 1,2,3-benzotriazin-4-ones are important structural motifs in synthetic and medicinal chemistry, valued for their distinctive frameworks and functional versatility. We have developed an efficient, one-pot strategy for the synthesis of N-arylated benzotriazoles and benzotriazinones. The protocol involves in situ diazotization of o-phenylenediamine or 2-aminobenzamide using tert-butyl nitrite (tBuONO), followed by trapping of arynes generated in situ from 2-(trimethylsilyl)aryltriflates in the presence of CsF. The methodology exhibits broad functional-group tolerance and was successfully applied to 47 substrates, affording yields in the range of 60-85%. Furthermore, gram-scale synthesis highlights the operational simplicity and practical utility of this approach.

1 aGhodake, Balaji, M.1 aBhattacharya, Asish, K. uhttps://library.ncl.res.in/content/one-pot-synthesis-n-arylated-benzotriazoles-and-benzotriazinones-situ-diazotization-and