01928nas a2200229 4500008004100000022001400041245008600055210006900141260000800210300001600218490000700234520116200241100002001403700002501423700002301448700001901471700002701490700002701517700002101544700001801565856011501583 2022 eng d a0020-166900aFirst-row transition metal complexes of a phosphine-silylene- based hybrid ligand0 aFirstrow transition metal complexes of a phosphinesilylene based cAUG a13330-133410 v613 a

We have prepared two new silylene-phosphine-based hybrid ligands Si{N(R)C6H4(PPh2)}{PhC((NBu)-Bu-t)(2)} [R = TMS {trimethylsilyl} (1) and TBDMS {tert-butyldimethylsilyl} (2)], which possess two donor sites. Furthermore, the treatment of the bidentate ligand 1 with base metal halides {FeBr2, CoBr2, NiCl(2)middotdme [nickel chloride(II) ethylene glycol dimethyl ether]} and 2 with NiBr(2)middotdme [nickel bromide(II) ethylene glycol dimethyl ether] afforded four-coordinate six-membered metal complexes 3-6, respectively, which feature coordination from both Si(II) and P(III) sites. Subsequently, complexes 3 [(FeBr2)Si{N(SiMe3)C6H4(PPh2)}{PhC((NBu)-Bu-t)(2)}], 4 [(CoBr2)Si{N(SiMe3)C6H4(PPh2)}{PhC((NBu)-Bu-t)(2)}], 5 [(NiCl2)Si{N(SiMe3)C6H4(PPh2)}{PhC((NBu)-Bu-t)(2)}], and 6 [(NiBr2)Si{N((SiBuMe2)-Bu-t)C6H4(PPh2)}{PhC((NBu)-Bu-t)(2)}] are studied for their redox and magnetic properties with the help of UV-vis spectroscopy, cyclic voltammetry, SQUID magnetometry, and theoretical calculations. Complexes 3-6 were found to display a paramagnetic behavior. All the compounds are well established by single-crystal X-ray diffraction studies.

1 aAkhtar, Ruksana1 aKaulage, Sandeep, H.1 aSangole, Mayur, P.1 aTothadi, Srinu1 aParvathy, Parameswaran1 aParameswaran, Pattiyil1 aSingh, Kirandeep1 aKhan, Shabana uhttps://library.ncl.res.in/content/first-row-transition-metal-complexes-phosphine-silylene-based-hybrid-ligand01202nas a2200181 4500008004100000022001400041245010700055210006900162260000900231300001400240490000700254520054100261100002500802700002000827700002400847700001800871856013100889 2024 eng d a1359-734500aHybrid silylene-Pd catalyst: efficient C-N cross-coupling of sterically bulky amines and chiral amines0 aHybrid silylenePd catalyst efficient CN crosscoupling of sterica cSEP  a9958-99610 v603 a

Herein, we report a catalytic system with N-heterocyclic silylene (NHSi)-phosphine-based hybrid bidentate ligands [PhC(NtBu)2SiN(PR2)(2,6-iPr2-C6H3)] and Pd(dba)2, which serves as an effective catalyst for C-N cross-coupling of a wide range of sterically bulky amines and optically active amines, which is challenging otherwise. Herein, we report a hybrid silylene-based bidentate ligand (SiNP)-Pd(0) catalytic system, which performs the C-N coupling of difficult substrates, e.g., sterically bulky amines and chiral amines.

1 aKaulage, Sandeep, H.1 aParvin, Nasrina1 aKhopade, Kishor, V.1 aKhan, Shabana uhttps://library.ncl.res.in/content/hybrid-silylene-pd-catalyst-efficient-c-n-cross-coupling-sterically-bulky-amines-and-chiral01595nas a2200205 4500008004100000022001400041245012900055210006900184260000800253300001400261490000700275520082600282100002901108700003001137700002301167700002801190700002501218700002101243856012501264 2025 eng d a1477-052000aRongalite-promoted self-dimerization of 3-acylidene-2-oxindoles: a diastereoselective route to synthesis of bispirooxindoles0 aRongalitepromoted selfdimerization of 3acylidene2oxindoles a dia cOCT a8687-86940 v233 a

A facile and efficient one-pot rongalite-mediated self-dimerization of 3-acylidene-2-oxindoles has been developed for the diastereoselective synthesis of highly functionalized dispirocyclopentanebisoxindoles. The reaction proceeds via a domino sequence involving intermolecular Michael addition followed by intramolecular aldol cyclization under basic conditions. Rongalite, an inexpensive and readily available reagent (similar to\$0.03 per g), plays a crucial role in promoting the transformation, offering significant advantages such as operational simplicity, step economy, scalability to gram-scale synthesis, and potential for post-functionalization. This methodology provides an efficient route to structurally complex oxindole frameworks with high stereocontrol, demonstrating broad synthetic utility.

1 aChaudhari, Suryakant, S.1 aNichinde, Chandrakant, B.1 aPatil, Baliram, R.1 aGirase, Amardipsing, S.1 aKaulage, Sandeep, H.1 aKinage, Anil, K. uhttps://library.ncl.res.in/content/rongalite-promoted-self-dimerization-3-acylidene-2-oxindoles-diastereoselective-route01079nas a2200205 4500008004100000022001400041245008300055210006900138260000800207300001600215490000700231520039700238100002500635700002200660700002300682700002100705700001700726700001800743856011200761 2025 eng d a1359-734500aSilylene-copper(i) catalysis: regioselective protoboration of terminal alkynes0 aSilylenecopperi catalysis regioselective protoboration of termin cDEC a19652-196550 v613 a

Herein, we report an efficient regioselective protoboration of the terminal alkynes catalyzed by newly synthesized silylene-copper(i)-aryl complexes. This method offers a broad substrate scope, good functional-group compatibility, and a gram-scale synthetic ability. The insight into the mechanistic cycle is also provided with the support of experimental and theoretical studies.

1 aKaulage, Sandeep, H.1 aShah, Brij, Kumar1 aPanday, Rishukumar1 aSharma, Himanshu1 aVanka, Kumar1 aKhan, Shabana uhttps://library.ncl.res.in/content/silylene-copperi-catalysis-regioselective-protoboration-terminal-alkynes