title: Reaction of alpha-(N-carbamoyl)alkylcuprates with propargyl substrates: synthetic route to alpha-amino allenes and delta3-pyrrolines.
abstract: [reaction: see text] Carbamate deprotonation followed by treatment with CuCN.2LiCl affords alpha-(N-carbamoyl)alkylcuprates which react with propargyl halides, mesylates, tosylates, phosphates, acetates, and epoxides to give alpha-(N-carbamoyl) allenes via an anti-S(N)2' substitution process. Propargyl halides, sulfonates, and phosphates give good yields of carbamoyl allenes, while the acetates afford low yields. Propargyl substrates undergo regiospecific S(N)2' substitution in the absence of severe steric hindrance. The alpha-(N-carbamoyl) allenes can be cyclized to 2-oxazolidinones or deprotected to afford the free amines which can be cyclized to Delta(3)-pyrrolines with either AgNO(3) or Ru(3)(CO)(12).
authors.affiliation: Department of Chemistry, Howard L. Hunter Laboratory, Clemson University, Clemson, South Carolina 29634-0973, USA.
authors.forename: R Karl
authors.initials: RK
authors.lastname: Dieter
authors.forename: Ningyi
authors.initials: N
authors.lastname: Chen
authors.forename: Huayun
authors.initials: H
authors.lastname: Yu
authors.forename: Lois E
authors.initials: LE
authors.lastname: Nice
authors.forename: Vinayak K
authors.initials: VK
authors.lastname: Gore
mesh_terms: D000466:Alkadienes / Q000138:chemical synthesis*; D000480:Alkynes / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D020005:Propanols / Q000737:chemistry*; D011758:Pyrroles / Q000138:chemical synthesis*
chemical_list: D000466:Alkadienes; D000480:Alkynes; D009942:Organometallic Compounds; D020005:Propanols; D011758:Pyrroles; D003300:Copper; C028255:propargyl alcohol