A highly enantioselective thiocarbonylation of styrenes with CO and thiols has been achieved by Pd catalysis, providing highly enantioenriched thioesters in good to excellent yields. Key to the successful execution of this reaction is the use of a chiral sulfoxide‐(P‐dialkyl)‐phosphine (SOP) ligands. This thiocarbonylation proceeds smoothly under mild reaction conditions (1 atm CO and 0 °C) and displays broad substrate scope. Also demonstrated is that this transformation can be conducted using surrogates of CO, greatly increasing the safety aspects of running the reaction. The generality and utility of the method is manifested by its application to the synthetic transformations of thioester products and the direct acylation of cysteine‐containing dipeptides. A primary mechanism was investigated and a plausible catalytic cycle was proposed.

An enantioselective Cu/Pd-catalyzed borylative coupling of styrenes with aryl/alkenyl iodides was realized using a chiral sulfoxide-phosphine (SOP) ligand. Enantioenriched 1,1-diarylethyl and β-aryl-homoallylic boronates are readily prepared. A streamlined procedure merging arylboration and subsequent Pd-catalyzed Suzuki–Miyaura cross-coupling enables the modular assembly of enantioenriched 1,1,2-triarylethanes, including two medicinally important chiral small-molecule targets.

A new Cu-catalyzed enantioselective three-component (i.e., styrenes, B2pin2, and propargylic phosphates) allenylation via an SN2′ substitution of propargylic electrophiles with vinylarene-derived chiral nucleophiles is presented. This method provides an efficient and enantioselective approach to access a range of optically pure di-(1,1-), tri-, and tetra-substituted allenes with α-central chirality and axial chirality in excellent chemo-, regio-, diastereo-, and enantioselectivities.

An enantioselective 1,4-borylstannation of 1,3-enynes employed a chiral sulfoxide phosphine (SOP)/Cu complex as a catalyst, and the desired products, chiral allenylstannes, were first synthesized by asymmetric catalysis with satisfactory yields and enantioselectivies.

Ah ighly enantioselective thiocarbonylation of styrenes with CO and thiols has been achieved by Pd catalysis, providing highly enantioenriched thioesters in good to excellent yields.Key to the successful execution of this reaction is the use of achiral sulfoxide-(P-dialkyl)-phosphine (SOP) ligands. This thiocarbonylation proceeds smoothly under mild reaction conditions (1 atm CO and 0 8 8C) and displays broad substrate scope.A lso demonstrated is that this transformation can be conducted using surrogates of CO,greatly increasing the safety aspects of running the reaction. The generality and utility of the method is manifested by its application to the synthetic transformations of thioester products and the direct acylation of cysteine-containing dipeptides.Ap rimary mechanism was investigated and aplausible catalytic cycle was proposed. Scheme 1. Pd-catalyzed enantioselective thiocarbonylation of alkenes. Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.Scheme 7. Proposed catalytic cycle.Figure 2. X-ray structure and DFT calculation.