Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.
J Am Chem Soc. 2011 Jun 1;133(21):8154-7. doi: 10.1021/ja203560q. Epub 2011 May 10.
A new family of stereoconvergent cross-couplings of unactivated secondary alkyl electrophiles has been developed, specifically, arylamine-directed alkyl-alkyl Suzuki reactions. This represents the first such investigation to be focused on the use of alkyl chlorides as substrates. Structure-enantioselectivity studies are consistent with the nitrogen, not the aromatic ring, serving as the primary site of coordination of the arylamine to the catalyst. The rate law for this asymmetric cross-coupling is compatible with transmetalation being the turnover-limiting step of the catalytic cycle.
现已开发出一种新的非活化仲烷基亲电试剂的立体汇聚交叉偶联家族，即芳基胺导向的烷基-烷基铃木反应。这是首次将氯化烷基作为底物进行此类研究。结构对映选择性研究表明，氮原子而不是芳环是芳基胺与催化剂配位的主要位点。这种不对称交叉偶联的速率定律与转金属化是催化循环的决速步骤相兼容。
