title: Photoreactions of 1-acetylisatin with alkynes: regioselectivity in oxetene formation and easy access to 3-alkylideneoxindoles and dispiro[oxindole[3,2']furan[3',3' ']oxindole]s.
abstract: [reaction: see text] Photoinduced reactions of 1-acetylisatin (IS) with diphenylacetylenes 1a-c, 1-(p-methoxyphenyl)propyne 2, and 1,4-diphenyl-1,3-butadiyne 3 gave beta,beta-disubstituted 3-alkylidene oxindoles 6-12 respectively via [2+2] cycloaddition of 3IS* with the alkyne and subsequent oxetene ring opening. Photoreactions of IS with phenylacetylenes 4a-d and cyclopropylacetylene 5 furnished the dispiroindole[3,2']furan[3',3' ']indoles 13 and 14. Compounds 13 and 14 are formed in tandem reactions initiated by [2+2] cycloaddition of 3IS* with the alkynes to give spirooxetenes Va and Vb, which upon spontaneous ring opening gave the alpha,beta-unsaturated aldehydes IVa and IVb. It is proposed that hydrogen abstraction of 3IS* from the C(O)-H functionality in IV followed by dissociation of the triplet isatin ketyl (A)-aldehyde acyl (B) radical pair and an oxygenphilic attack of the acyl radical B at the C3 carbonyl oxygen atom of a neutral IS gave the 2:1 (IS:4) radical C, which took part in an intramolecular radical cyclization to give the dispiroindole[3,2']furan[3',3' ']indoles 13 and 14. The regioselectivity in the [2+2] photocycloadditions of IS with 4 to afford the oxetene Va depends on the intervening of the more stable 1,4-diradical intermediates VI, which have a linear alpha-phenyl-substituted vinyl radical where the phenyl provides spin delocalization of the radical center at the sp carbon atom.
authors.affiliation: Department of Chemistry, Nanjing University, Nanjing 210093, People's Republic of China.
authors.forename: Lei
authors.initials: L
authors.lastname: Wang
authors.forename: Yan
authors.initials: Y
authors.lastname: Zhang
authors.forename: Hua-You
authors.initials: HY
authors.lastname: Hu
authors.forename: Hoong Kun
authors.initials: HK
authors.lastname: Fun
authors.forename: Jian-Hua
authors.initials: JH
authors.lastname: Xu
mesh_terms: D000114:Acetylene / Q000737:chemistry* / Q000378:metabolism; D005663:Furans / Q000737:chemistry*; D007211:Indoles / Q000737:chemistry*; D007510:Isatin / Q000031:analogs & derivatives* / Q000737:chemistry* / Q000378:metabolism; D010777:Photochemistry; D013237:Stereoisomerism
chemical_list: D005663:Furans; D007211:Indoles; C414384:1-acetylisatin; D007510:Isatin; D000114:Acetylene