Enantioselective copper catalysed C-H insertion reaction of 2-sulfonyl-2-diazoacetamides to form gamma-lactams

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TY  - JOUR
  - Clarke, LA,Ring, A,Ford, A,Sinha, AS,Lawrence, SE,Maguire, AR
  - 2014
  - December
  - Organic ; Biomolecular Chemistry
  - Enantioselective copper catalysed C-H insertion reaction of 2-sulfonyl-2-diazoacetamides to form gamma-lactams
  - Validated
  - WOS: 15 ()
  - ALPHA-DIAZOACETAMIDES INTRAMOLECULAR ADDITION CARBENE INSERTION DIASTEREOSELECTIVITY TRANSFORMATIONS DIAZOSULFONES DIRHODIUM(II) STEREOCONTROL CYCLIZATION SELECTIVITY
  - 12
  - 7612
  - 7628
  - The first examples of asymmetric copper-catalysed intramolecular C-H insertion reactions of 2-sulfonyl-2-diazoacetamides are described; trans gamma-lactams with up to 82% ee are achieved with the CuCl2-bisoxazoline-NaBARF catalyst system. The reactions generally display high efficiency and high trans selectivity, and also a strong regiochemical preference for insertion to lead to the formation of 5-membered rings over 4-membered rings. In cases where there are competing C-H insertion pathways available, to form sulfolanes or thiopyrans, only the insertion into the amide chain to form gamma-lactams is observed. With phenylsulfonyl derivatives, a minor competing C-H insertion pathway leading to beta-lactams is seen; interestingly, changing the identity of the copper ligand changes the product ratio of beta/gamma-lactams. The copper catalysed reactions compare favorably in terms of efficiency and enantioselectivity to the corresponding reactions catalysed by commercially available chiral rhodium catalysts.
  - 10.1039/c4ob01430h
DA  - 2014/12
ER  - 
@article{V279269068,
   = {Clarke,  LA and Ring,  A and Ford,  A and Sinha,  AS and Lawrence,  SE and Maguire,  AR },
   = {2014},
   = {December},
   = {Organic ; Biomolecular Chemistry},
   = {Enantioselective copper catalysed C-H insertion reaction of 2-sulfonyl-2-diazoacetamides to form gamma-lactams},
   = {Validated},
   = {WOS: 15 ()},
   = {ALPHA-DIAZOACETAMIDES INTRAMOLECULAR ADDITION CARBENE INSERTION DIASTEREOSELECTIVITY TRANSFORMATIONS DIAZOSULFONES DIRHODIUM(II) STEREOCONTROL CYCLIZATION SELECTIVITY},
   = {12},
  pages = {7612--7628},
   = {{The first examples of asymmetric copper-catalysed intramolecular C-H insertion reactions of 2-sulfonyl-2-diazoacetamides are described; trans gamma-lactams with up to 82% ee are achieved with the CuCl2-bisoxazoline-NaBARF catalyst system. The reactions generally display high efficiency and high trans selectivity, and also a strong regiochemical preference for insertion to lead to the formation of 5-membered rings over 4-membered rings. In cases where there are competing C-H insertion pathways available, to form sulfolanes or thiopyrans, only the insertion into the amide chain to form gamma-lactams is observed. With phenylsulfonyl derivatives, a minor competing C-H insertion pathway leading to beta-lactams is seen; interestingly, changing the identity of the copper ligand changes the product ratio of beta/gamma-lactams. The copper catalysed reactions compare favorably in terms of efficiency and enantioselectivity to the corresponding reactions catalysed by commercially available chiral rhodium catalysts.}},
   = {10.1039/c4ob01430h},
  source = {IRIS}
}
AUTHORSClarke, LA,Ring, A,Ford, A,Sinha, AS,Lawrence, SE,Maguire, AR
YEAR2014
MONTHDecember
JOURNAL_CODEOrganic ; Biomolecular Chemistry
TITLEEnantioselective copper catalysed C-H insertion reaction of 2-sulfonyl-2-diazoacetamides to form gamma-lactams
STATUSValidated
TIMES_CITEDWOS: 15 ()
SEARCH_KEYWORDALPHA-DIAZOACETAMIDES INTRAMOLECULAR ADDITION CARBENE INSERTION DIASTEREOSELECTIVITY TRANSFORMATIONS DIAZOSULFONES DIRHODIUM(II) STEREOCONTROL CYCLIZATION SELECTIVITY
VOLUME12
ISSUE
START_PAGE7612
END_PAGE7628
ABSTRACTThe first examples of asymmetric copper-catalysed intramolecular C-H insertion reactions of 2-sulfonyl-2-diazoacetamides are described; trans gamma-lactams with up to 82% ee are achieved with the CuCl2-bisoxazoline-NaBARF catalyst system. The reactions generally display high efficiency and high trans selectivity, and also a strong regiochemical preference for insertion to lead to the formation of 5-membered rings over 4-membered rings. In cases where there are competing C-H insertion pathways available, to form sulfolanes or thiopyrans, only the insertion into the amide chain to form gamma-lactams is observed. With phenylsulfonyl derivatives, a minor competing C-H insertion pathway leading to beta-lactams is seen; interestingly, changing the identity of the copper ligand changes the product ratio of beta/gamma-lactams. The copper catalysed reactions compare favorably in terms of efficiency and enantioselectivity to the corresponding reactions catalysed by commercially available chiral rhodium catalysts.
PUBLISHER_LOCATION
ISBN_ISSN
EDITION
URL
DOI_LINK10.1039/c4ob01430h
FUNDING_BODY
GRANT_DETAILS