Herein the first organocatalytic atroposelective synthesis of BINAM derivatives is detailed. The findings of which inspired the development of new methodology directed toward the synthesis of 3-substituted-2-nitronaphthalene building blocks. The nitronaphthalenes were then utilized in a new approach aimed at the synthesis of symmetrical and unsymmetrical diaryl hydrazines. A novel approach for the synthesis of functionalized, non-C2-symmetric, atropisomeric biaryls in a one-pot transformation is also described.