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1. Organocatalytic Asymmetric Synthesis of Si-Stereogenic Siloxanols

   https://doi.org/10.1021/acscatal.3c03932  

   Dalton, Jacob J.; Bernal Sánchez, Adilene; Kelly, Austin T.; Fettinger, James C.; Franz, Annaliese K. (January 2024, ACS Catalysis)
2. Asymmetric Synthesis of P-Stereogenic Secondary Phosphine ­Oxides (SPOs)

   https://doi.org/10.1055/a-1582-0169  

   Glueck, David S. (January 2022, Synthesis)

   Abstract P-Stereogenic secondary phosphine oxides [SPOs, RR′P(O)H], valuable ligands for metal complexes in asymmetric catalysis, are also building blocks for other chiral phosphorus derivatives. This short review summarizes methods used for asymmetric synthesis of P-stereogenic SPOs. 1 Introduction 2 Configurational Stability of P-Stereogenic SPOs 3 Classical Resolution, HPLC Separation, and Dynamic Resolution 4 Synthesis via Chiral Auxiliaries 5 Kinetic Resolution 6 Conclusions and Outlook 

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3. Control of stereogenic oxygen in a helically chiral oxonium ion

   https://doi.org/10.1038/s41586-023-05719-z  

   Smith, Owen; Popescu, Mihai V.; Hindson, Madeleine J.; Paton, Robert S.; Burton, Jonathan W.; Smith, Martin D. (March 2023, Nature)

   Abstract The control of tetrahedral carbon stereocentres remains a focus of modern synthetic chemistry and is enabled by their configurational stability. By contrast, trisubstituted nitrogen 1 , phosphorus 2 and sulfur compounds 3 undergo pyramidal inversion, a fundamental and well-recognized stereochemical phenomenon that is widely exploited 4 . However, the stereochemistry of oxonium ions—compounds bearing three substituents on a positively charged oxygen atom—is poorly developed and there are few applications of oxonium ions in synthesis beyond their existence as reactive intermediates 5,6 . There are no examples of configurationally stable oxonium ions in which the oxygen atom is the sole stereogenic centre, probably owing to the low barrier to oxygen pyramidal inversion 7 and the perception that all oxonium ions are highly reactive. Here we describe the design, synthesis and characterization of a helically chiral triaryloxonium ion in which inversion of the oxygen lone pair is prevented through geometric restriction to enable it to function as a determinant of configuration. A combined synthesis and quantum calculation approach delineates design principles that enable configurationally stable and room-temperature isolable salts to be generated. We show that the barrier to inversion is greater than 110 kJ mol −1 and outline processes for resolution. This constitutes, to our knowledge, the only example of a chiral non-racemic and configurationally stable molecule in which the oxygen atom is the sole stereogenic centre. 

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4. P-stereogenic N-vinylphosphonamides enabled by asymmetric allylic substitution-isomerization

   https://doi.org/10.1016/j.xcrp.2021.100594  

   Zhang, Xiu-Lian; Qi, Xiaotian; Wu, Ying-Xiang; Liu, Peng; He, Ying (October 2021, Cell Reports Physical Science)
5. Protonation of P-Stereogenic Phosphiranes: Phospholane Formation via Ring Opening and C–H Activation

   https://doi.org/10.1021/acsomega.3c00885  

   Tipker, Ryan M.; Muldoon, Jake A.; Jo, Jacob; Connors, Christopher S.; Varga, Balazs R.; Hughes, Russell P.; Glueck, David S. (March 2023, ACS Omega)