title: Stereoselective and diversity-oriented synthesis of trisubstituted allylic alcohols and amines.
abstract: Stereoselective and diversity-oriented synthesis of trisubstituted olefins was achieved by using ortho-diphenylphosphanyl benzoate (o-DPPB) as a directing group for allylic substitution. The starting point of this methodology was a set of α-methylene aldehydes derived from Baylis-Hillman adducts. Subsequent addition of different organometallic reagents led to a variety of allylic alcohol substrates. After introduction of the reagent-directing o-DPPB group, copper-mediated allylic substitution with a wide range of Grignard reagents enabled the stereoselective construction of a large number of E-configured trisubstituted allylic alcohols and amines in excellent yields and stereoselectivities. Remarkable is the synthetic flexibility, which allows a wide range of permutations starting from an aldehyde followed by successive introduction of the substituents R(2) and R(3) from organometallic Grignard based reagents. Thus, starting from only a few precursors, a diversity-oriented synthesis of stereodefined trisubstituted allylic alcohols and amines becomes possible.
authors: Institut für Organische Chemie und Biochemie, Freiburg Institute for Advances Studies (FRIAS), Universität Freiburg, Albertstr. 21, Germany.
authors: Yvonne
authors: Y
authors: Schmidt
authors: Bernhard
authors: B
authors: Breit
mesh_terms: D000588:Amines / Q000138:chemical synthesis* / Q000737:chemistry; D001565:Benzoates / Q000737:chemistry*; D001713:Biphenyl Compounds / Q000737:chemistry*; D003300:Copper; D007202:Indicators and Reagents / Q000737:chemistry*; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D020005:Propanols / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D000588:Amines; D001565:Benzoates; D001713:Biphenyl Compounds; D007202:Indicators and Reagents; D009942:Organometallic Compounds; D020005:Propanols; C544846:o-diphenylphosphanylbenzoyl; C006463:allyl alcohol; D003300:Copper