One-Step Construction of Atropisomers Bearing 1,5-Central\nand Axial Chirality via Catalytic Diastereo- and Atroposelective Remote\nDesymmetrizing Alkynylation

Catalytic\nasymmetric construction of atropisomers with multiple\nstereogenic elements has recently become an emerging area. However,\ngeneral methods that produced atropisomers bearing remote 1,5-axial\nand central chirality efficiently and stereoselectively are scarce\nyet highly challenging. We herein report a catalytic diastereo- and\natroposelective remote desymmetrizing alkynylation of axially prochiral\ndialkynes with <i>ortho</i>-quinone methides (<i>o</i>-QMs), furnishing atropisomers bearing 1,5-remote centrally and axially\nstereogenic elements. The remote control of prochiral axis far from\nthe reaction site could be simultaneously achieved during the stereoselective\nC(sp<sup>3</sup>)–C(sp) bond-forming process to generate a\nstereogenic center. In addition, a kinetic resolution of axially racemic\nalkynes via diastereo- and atroposelective remote alkynylation with <i>o</i>-QMs has been developed, further enriching structural diversity\nof atropisomers bearing 1,5-central and axial chirality. The present\nmethod expands the chemical space of atropisomeric molecules bearing\nmultiple chiral elements by facile downstream diversification of C–C\ntriple bonds. Finally, the alkynylation of <i>o</i>-QMs\ncan also be applied for the construction of chiral motifs bearing\n1,9- and 1,10-stereogenic centers.