1-alkoxyallene as an effective precursor for regio- and stereocontrolled allylation reactions with aliphatic aldehydes via bis-stannylation.
Bis-stannylation of 1-(methoxy)methoxyallene yields (E)-(3-(methoxymethoxy)prop-2-ene-1,2-diyl) bis-tributylstannane (2) as a highly reactive allylation reagent. Stereoselective reactions of functionalized stannane 2 with a variety of aldehydes provide good yields of 1,2-diol derivatives. Reactions with alpha-alkoxyaldehydes proceed with chelation-controlled addition to afford efficient constructions of 3,4-anti-4,5-syn-relationships in stereotriads bearing three differentiated oxygen (alkoxy and hydroxy) substituents. Mechanistic considerations are presented, and derivatives for NMR experiments support the stereochemical assignments. An X-ray diffraction study is included.
Williams
David R
DR
Department of Chemistry, Indiana University, Bloomington, Indiana 47405-7102, USA. williamd@indiana.edu
Fultz
Micheal W
MW
D000447:Aldehydes / Q000138:chemical synthesis / Q000737:chemistry*; D000475:Alkenes / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism; D014001:Tin / Q000737:chemistry*
C507239:(E)-(3-(methoxymethoxy)prop-2-ene-1,2-diyl) bis-tributylstannane; D000447:Aldehydes; D000475:Alkenes; D009942:Organometallic Compounds; D014001:Tin