01461nas a2200241 4500008004100000022001400041245014600055210006900201260000800270300001400278490000800292520058100300653001600881653002800897653001800925653001800943653002500961100002500986700002801011700002701039700002601066856012701092 2020 eng d a1615-415000aPd-catalyzed annulation of beta-iodovinyl sulfones with 2-halophenols: a general route for the synthesis of 3-sulfonyl benzofuran derivatives0 aPdcatalyzed annulation of betaiodovinyl sulfones with 2halopheno cMAR a1317-13220 v3623 a

The palladium-catalyzed annulation between beta-iodovinyl sulfones and 2-halophenols or 1-bromo-2-naphthol or 2-bromo-3-pyridinol is presented. The annulation process involving oxa-Michael addition-elimination and intramolecular Heck reaction leading to form 2,3-disubstituted benzofurans (aryl benzofuryl sulfones) in good to high yields. The regioselective tandem construction of C-O and C-C bonds has been achieved with a variety of substitution patterns. Moreover, the tandem process is reliable at gram-scale reactions and a plausible mechanism is also proposed.

10aBenzofurans10abeta-Iodovinyl sulfones10aHeck reaction10aNaphthofurans10aoxa-Michael addition1 aReddy, Raju, Jannapu1 aKumar, Jangam, Jagadesh1 aKumari, Arram, Haritha1 aKrishna, Gamidi, Rama uhttps://library.ncl.res.in/content/pd-catalyzed-annulation-beta-iodovinyl-sulfones-2-halophenols-general-route-synthesis-301952nas a2200217 4500008004100000022001400041245018200055210006900237260000900306520106300315653002101378653004201399653001901441653002201460653002301482100002701505700002801532700002601560700002501586856012301611 2021 eng d a0039-788100aNickel-catalyzed difunctionalization of alkynyl bromides with thiosulfonates and N-arylthio succinimides: a convenient synthesis of 1,2-thiosulfonylethenes and 1,1-dithioethenes0 aNickelcatalyzed difunctionalization of alkynyl bromides with thi cAPR 3 a

An efficient nickel-catalyzed vicinal thiosulfonylation of 1bromoalkynes with thiosulfonates in the presence of cesium carbonate is described. An operationally simple and highly regioselective atom transfer radical addition (ATRA) of alkynyl bromides provides a wide range of (E)-1,2-thiosulfonylethenes (alpha-aryl-beta-thioarylvinyl sulfones) in moderate to high yields. The extensive substrate scope of both alkynyl bromides and thiosulfonates is explored with a broad range of functional groups. Indole-derived 1,1- bromoalkenes were also successfully explored in this 1,2-thiosulfonylation process. Moreover, the nickel-catalyzed geminal- dithiolation of alkynyl bromides with N-arylthio succinimides provides 1,1-dithioalkenes in high yields. The present protocol is reliable on gram scale, and a sequential one-pot bromination and thiosulfonylation of phenylacetylene is achieved in a scale-up synthesis. Following control experiments, a plausible mechanism is proposed to rationalize the experimental outcome and the vicinal thiosulfonylation.

10aalkynyl bromides10aatom transfer radical addition (ATRA)10athiosulfonates10athiosulfonylation10avinyl thiosulfones1 aKumari, Arram, Haritha1 aKumar, Jangam, Jagadesh1 aKrishna, Gamidi, Rama1 aReddy, Raju, Jannapu uhttps://library.ncl.res.in/content/nickel-catalyzed-difunctionalization-alkynyl-bromides-thiosulfonates-and-n-arylthio01585nas a2200241 4500008004100000022001400041245017600055210006900231260000800300300001200308490000800320520067300328653003201001653002001033653003101053653001501084653001901099100002501118700001501143700002701158700002601185856013201211 2022 eng d a1615-415000aInterrupted CuAAC-thiolation for the construction of 1,2,3-triazole-fused eight-membered heterocycles from O-/N-propargyl derived benzyl thiosulfonates with organic azides0 aInterrupted CuAACthiolation for the construction of 123triazolef cJAN a319-3250 v3643 aA copper(I)-catalyzed interrupted click-sulfenylation of O-/N-propargyl benzyl thiosulfonates with organic azides has been disclosed. The unified CuAAC-thiolation provides a wide range of triazole-fused eight-membered heterocycles in good to high (51-94%) yields under mild reaction conditions. Moreover, a three-component reaction is also achieved involving O-/N-propargyl benzyl thiosulfonates, benzyl bromide, and sodium azide to deliver fused-triazoles in 61-74% yields. From a synthetic point of view, the present protocol has been demonstrated at gram-scale reactions. A plausible mechanism is also proposed based on experimental results and control experiments.10aEight-Membered Heterocycles10aFused-Triazoles10aInterrupted-Click Reaction10aThiolation10athiosulfonates1 aReddy, Raju, Jannapu1 aWaheed, Md1 aKumari, Arram, Haritha1 aKrishna, Gamidi, Rama uhttps://library.ncl.res.in/content/interrupted-cuaac-thiolation-construction-123-triazole-fused-eight-membered-heterocycles-o-n02045nas a2200181 4500008004100000022001400041245016200055210006900217260000800286300001400294490000700308520132400315100002501639700002701664700002301691700002601714856012301740 2022 eng d a0022-326300aSolvent-driven mono- and bis-sulfenylation of (E)-beta-iodovinyl sulfones with thiols for flexible synthesis of 1,2-thiosulfonylalkenes and 1,2-dithioalkenes0 aSolventdriven mono and bissulfenylation of Ebetaiodovinyl sulfon cMAR a3934-39510 v873 a

The nature of solvent is a key factor for stereoselective mono-and bis-thiolation of (E)-beta-iodovinyl sulfones with thiols under basic conditions. A novel and unprecedented vicinal bisthiolation of (E)-beta-iodovinyl sulfones with thiols under the influence of K2CO3/DMSO at room temperature for quick assembly of (E)-1,2-dithio-1-alkenes is presented. Solvent-induced stereoselective monosulfenylation of (E)-beta-iodovinyl sulfones with thiols has also been established for the synthesis of both (E)- and (Z)-1,2-thiosulfonylethenes in MeCN and MeOH, respectively. Moreover, K2CO3-mediated desulfonylative-sulfenylation of (Z)-1,2-thiosulfonylethenes with thiols in DMSO furnished unsymmetrical (Z)-1,2-dithio-1-alkenes for the first time. The solvent-dependent versatile reactivity of (E)-beta-iodovinyl sulfones has been successfully explored to provide a set of (E)-/(Z)-1,2-dithio-1-alkenes and (E)-/(Z)-1,2-thiosulfonyl-1-alkenes in good to high yields with excellent stereoselectivities. Notably, this operationally simple process utilizes a broad substrate scope with good functional group tolerance and compatibility. The efficacy of the process has been proven for gram-scale reactions, and plausible mechanistic models are outlined on the basis of experimental results and control experiments.

1 aReddy, Raju, Jannapu1 aKumari, Arram, Haritha1 aSharadha, Nunavath1 aKrishna, Gamidi, Rama uhttps://library.ncl.res.in/content/solvent-driven-mono-and-bis-sulfenylation-e-beta-iodovinyl-sulfones-thiols-flexible