Enantiodivergent Synthesis of Both ()- and ()-Heteroaryl Aldols by Rationally Engineered Aldolases.

Aldolases, especially 2-deoxyribose-5-phosphate aldolase (DERA) enzymes, have been widely employed to access key chiral precursors for various active pharmaceutical ingredients (APIs). This has been enabled by expanding their substrate scope toward non-natural acceptors and donors via protein engineering. In this study, we endeavored to broaden the acceptor substrate scope of DERA from sp.

Divergent Approach to Highly Substituted Arenes via [3 + 3] Annulation of Vinyl Sulfoxonium Ylides with Ynones.

Herein, we report the divergent benzannulation for highly substituted arenes using vinyl sulfoxonium ylides and ynones. The addition of ynone at the γ-position of vinyl sulfoxonium ylides leads to dienyl sulfoxonium ylide that can undergo selective annulation under different conditions to give -terphenyls and parabens. Moreover, control experiments and quantum chemical calculations reveal two distinct reaction mechanisms for both annulations.

Synthesis and Applications of π-Conjugation-Extended Vinyl Sulfoxonium Ylides.

Herein, we report the synthesis of π-conjugation-extended vinyl sulfoxonium ylides from vinyl sulfoxonium ylide and electron-deficient alkynes. The new dienoate ylides are used in various transformations, such as X-H (X = S, O) insertion, halogenation, carbene-mediated transformation, and radical-mediated reductions to obtain a variety of conjugated dienoates.

Insights into the multifaceted applications of vinyl sulfoxonium ylides.

Sulfoxonium ylides are important synthetic precursors in various organic transformations. Their synthetic potential was well explored in the synthesis of various bioactive natural products and pharmaceuticals. Vinyl sulfoxonium ylide is a stabilized sulfoxonium ylide containing an electron-deficient alkene at the ylidic carbon.