title: Rhodium(II)-catalyzed alkyne amination of homopropargylic sulfamate esters: stereoselective synthesis of functionalized norcaradienes by arene cyclopropanation.
abstract: A rhodium(II) catalyzed nitrene-alkyne cycloaddition of stereochemically well-defined homopropargylic ethers is followed by arene cyclopropanation to afford unique tetracyclic norcaradiene products bearing a cyclic sulfamate. Products from the arene cyclopropanation (Buchner reaction) can be converted to fused cycloheptatrienes via a ring enlarging electrocyclization after nucleophilic ring opening of the cyclic sulfamate ester.
authors: Department of Chemistry, Center for Chemical Methodology and Library Development (CMLD-BU), Boston University , 590 Commonwealth Avenue, Boston, Massachusetts 02215, United States.
authors: Ryan A
authors: RA
authors: Brawn
authors: Kaicheng
authors: K
authors: Zhu
authors: James S
authors: JS
authors: Panek
mesh_terms: D000480:Alkynes / Q000737:chemistry*; D000586:Amination; D002384:Catalysis; D003500:Cyclization; D003508:Cycloheptanes / Q000138:chemical synthesis* / Q000737:chemistry; D003521:Cyclopropanes / Q000737:chemistry*; D004952:Esters; D007097:Imines / Q000737:chemistry; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D012238:Rhodium / Q000737:chemistry*; D013237:Stereoisomerism; D013451:Sulfonic Acids / Q000737:chemistry*
chemical_list: D000480:Alkynes; D003508:Cycloheptanes; D003521:Cyclopropanes; D004952:Esters; D007097:Imines; D009942:Organometallic Compounds; D013451:Sulfonic Acids; C017621:phenylnitrene; D012238:Rhodium