Department of Biochemistry, University of Texas Southwestern Medical Center, 5323 Harry Hines Boulevard, Dallas, Texas 75398-9038, United States.
J Am Chem Soc. 2011 Nov 16;133(45):18066-9. doi: 10.1021/ja207748r. Epub 2011 Oct 21.
We demonstrate that allenes, chiral 1,2-dienes, appended with basic functionality can serve as ligands for transition metals. We describe an allene-containing bisphosphine that, when coordinated to Rh(I), promotes the asymmetric addition of arylboronic acids to α-keto esters with high enantioselectivity. Solution and solid-state structural analysis reveals that one olefin of the allene can coordinate to transition metals, generating bi- and tridentate ligands.
我们证明了带有碱性官能团的丙二烯,手性 1,2-二烯,可用作过渡金属的配体。我们描述了一种含有丙二烯的双膦配体,当与 Rh(I)配位时,它能促进芳基硼酸对α-酮酯的不对称加成,具有高对映选择性。溶液和固态结构分析表明,丙二烯的一个烯烃可以与过渡金属配位,生成双齿和三齿配体。