01682nas a2200205   4500008004100000022001400041245011900055210006900174260000800243300001400251490000700265520092200272100002101194700002901215700002501244700002301269700002601292700002801318856013001346       2023                        eng d  a0022-326300aCatalyst-assisted selective vinylation and methylallylation of a quaternary carbon center using tert-butyl acetate0 aCatalystassisted selective vinylation and methylallylation of a   cJUL  a9686-97030 v883 a<p>
	The In-(OTf)(3)-catalyzed &amp; alpha;-vinylationof varioushydroxy-functionalized quaternary carbon centers using in situ generatedisobutylene from tert-butyl acetate is presentedas a novel synthetic methodology. Moreover, tert-butylacetate is a nonflammable feed stock and is a readily available sourcefor the in situ production of vinyl substituents, as demonstratedby the vinylation reaction with quaternary hydroxy/methoxy compounds.Moreover, an excellent selectivity for methylallylation over vinylationwas obtained with Ni-(OTf)(2) as a catalyst. In the case ofperoxyoxindole, methylallyl-functionalized 1,4-benzoxazin-3-one derivativeswere formed through the sequential rearrangement of peroxyoxindolefollowed by the nucleophilic attack by isobutylene. The detailed mechanismfor this reaction and rationalization for the selectivity are providedusing kinetics and density functional theory studies.</p>
1 aMohanta, Nirmala1 aSamal, Pragnya, Paramita1 aPandey, Akanksha, M.1 aMondal, Shankhajit1 aKrishnamurty, Sailaja1 aGnanaprakasam, Boopathy  uhttps://library.ncl.res.in/content/catalyst-assisted-selective-vinylation-and-methylallylation-quaternary-carbon-center-using