N-N axially chiral biaryls represent a rarely explored class of atropisomers. Reported herein is construction of diverse classes of diaxially chiral biaryls containing N-N and C-N/C-C diaxes in distal positions in excellent enantioselectivity and diastereoselectivity. The N-N chiral axis in the products provides a handle toward solvent-driven diastereodivergence, as has been realized in the coupling of a large scope of benzamides and sterically hindered alkynes, affording diaxes in complementary diastereoselectivity. The diastereodivergence has been elucidated by computational studies which revealed that the hexafluoroisopropanol (HFIP) solvent molecule participated in an unusual manner as a solvent as well as a ligand and switched the sequence of two competing elementary steps, resulting in switch of the stereoselectivity of the alkyne insertion and inversion of the configuration of the C-C axis. Further cleavage of the N-directing group in the diaxial chiral products transforms the diastereodivergence to enantiodivergence.

NN 轴向手性联芳基代表了一类很少被探索的阻转异构体。本文报道了不同类别的双轴手性联芳基化合物的构建，其中在远端位置含有 NN 和 CN/CC 二轴，具有优异的对映选择性和非对映选择性。产品中的 NN 手性轴提供了解决溶剂驱动的非对映发散的方法，正如在大量苯甲酰胺和空间位阻炔烃的偶联中所实现的那样，提供了互补非对映选择性的双轴。非对映发散已通过计算研究得到阐明，该研究表明六氟异丙醇（HFIP）溶剂分子以一种不寻常的方式作为溶剂和配体参与，并转换了两个竞争基本步骤的顺序，从而导致炔烃立体选择性的转换CC 轴配置的插入和反转。双轴手性产物中N-定向基团的进一步裂解将非对映体发散转变为对映体发散。