title: Asymmetric palladium-catalyzed umpolung cyclization of allylic acetate-aldehyde using formate as a reductant.
abstract: Palladium/chiral diphosphine-catalyzed umpolung cyclization of allylic acetate-aldehyde using formate as a terminal reductant affords cis-disubstituted pyrrolidine, tetrahydrofuran, and spiro carbocycle in high enantioselectivity. The formate does not cause allylpalladium reduction under the catalysis. The highly stereoselective cyclization would proceed through a cationic η(1)-allylpalladium ligated by diphosphine.
authors: Graduate School of Pharmaceutical Sciences, Tohoku University, Aramaki-aza aoba 6-3, Aoba-ku, Sendai 980-8578, Japan. hirokazu@mail.pharm.tohoku.ac.jp.
authors: Hirokazu
authors: H
authors: Tsukamoto
authors: Ayumu
authors: A
authors: Kawase
authors: Takayuki
authors: T
authors: Doi
mesh_terms: D000085:Acetates / Q000737:chemistry*; D000447:Aldehydes / Q000737:chemistry*; D000498:Allyl Compounds / Q000737:chemistry*; D002384:Catalysis; D003500:Cyclization; D005663:Furans / Q000138:chemical synthesis / Q000737:chemistry; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D010165:Palladium / Q000737:chemistry*; D010720:Phosphines / Q000737:chemistry; D011759:Pyrrolidines / Q000138:chemical synthesis / Q000737:chemistry; D019163:Reducing Agents / Q000138:chemical synthesis* / Q000737:chemistry; D013141:Spiro Compounds / Q000138:chemical synthesis / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D000085:Acetates; D000447:Aldehydes; D000498:Allyl Compounds; D005663:Furans; D009942:Organometallic Compounds; D010720:Phosphines; D011759:Pyrrolidines; D019163:Reducing Agents; D013141:Spiro Compounds; C018674:tetrahydrofuran; D010165:Palladium; C498551:allyl acetate; C032519:pyrrolidine