Organocatalyzed Dual Symmetry Breaking Enables Remote Construction of 1,5‐Heteroatom (Sulfur/Boron) Stereogenic Architectures

Comprehensive Summary Remote construction of dual heteroatom‐stereogenic architectures in a single catalytic process remains a fundamental challenge in heteroatom stereochemistry, as it requires the simultaneous and selective control of two distinct, spatially separated heteroatom stereocenters. Here, we report an organocatalyzed dual symmetry‐breaking strategy that enables the one‐step synthesis of remote 1,5‐heteroatom (sulfur/boron) dual‐stereogenic molecules (45 examples, up to 99% yield, 99% ee , and > 20:1 dr ), affording a versatile fluorescent platform with tunable emission and displaying potential stereochemistry‐dependent photosensitizing activity toward cancer cell ablation. DFT studies suggest that the multifunctional nature of the phase‐transfer catalyst underlies its enantio‐ and diastereoselective control.