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Initiation of radical cyclisation reactions using dimanganese decacarbonyl. A flexible approach to preparing 5-membered rings

Research output: Contribution to journalArticle

Author(s)

  • B C Gilbert
  • W Kalz
  • C I Lindsay
  • P T McGrail
  • A F Parsons
  • D T E Whittaker

Department/unit(s)

Publication details

JournalJournal of the Chemical Society-Perkin Transactions 1
DatePublished - 2000
Issue number8
Number of pages8
Pages (from-to)1187-1194
Original languageEnglish

Abstract

Photolysis of dimanganese decacarbonyl [Mn-2(CO)(10)] using visible light produces the manganese pentacarbonyl radical [Mn-.(CO)(5)] which reacts with organohalides to form carbon-centred radicals. Efficient halogen-atom abstraction occurs with allylic or benzylic halides or polyhalogenated precursors bearing a weak carbon-halogen bond. Steric interactions are also important and primary halides generally react much faster with Mn-.(CO)(5) than secondary or tertiary halides. The carbon-centred radicals can undergo efficient dimerisation or, in the presence of an acceptor double bond, cyclisation to form 5-membered rings. Cyclisation of terminal alkenes leads to primary radicals, which can then react by iodine- or bromine-atom transfer or, on addition of propan-2-ol, hydrogen-atom transfer. Hydroxylamines can also be formed when cyclisation reactions are carried out in the presence of TEMPO. These high-yielding cyclisation-trapping reactions are initiated under mild reaction conditions and the manganese halide by-products [of type XMn(CO)(5)] can be easily separated from products by a simple DBU work-up procedure.

    Research areas

  • CYCLIZATION REACTIONS, ALKYLATION SUBUNITS, ATOM TRANSFER, 1,6-DIENES, CARBONYL, CC-1065, LACTAMS, CATION, BONDS, CBI

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