Marshall J A, Schaaf G M
Department of Chemistry, University of Virginia, Charlottesville, VA 22904, USA.
J Org Chem. 2001 Nov 16;66(23):7825-31. doi: 10.1021/jo015936k.
The addition of (P)- and (M)-allenylzinc reagents, prepared in situ through Pd-catalyzed metalation of (R)- and (S)-3-butyn-2-ol mesylates, to diastereomeric stereotriad aldehydes 8, 13, 18, and 23 of syn,syn, syn,anti, anti,anti, and anti,syn stereochemistry was examined. Additions to the former two aldehydes afforded the four anti adducts with high diastereoselectivity and negligible mismatching. Significant mismatching was observed with the latter two aldehydes and the (M)-allenylzinc reagent. An evaluation of possible transition states is presented in consideration of steric and dipolar control elements.
研究了通过钯催化（R）-和（S）-3-丁炔-2-醇甲磺酸酯的金属化原位制备的（P）-和（M）-烯丙基锌试剂与顺式、顺式、顺式、反式、反式、反式和反式、顺式立体化学的非对映立体三联醛8、13、18和23的加成反应。前两种醛的加成反应以高非对映选择性和可忽略不计的错配得到了四种反式加合物。后两种醛与（M）-烯丙基锌试剂反应时观察到明显的错配。考虑到空间和偶极控制因素，对可能的过渡态进行了评估。
