# Iridium-Catalyzed Stereoselective α‑Alkylation of α‑Hydroxy Ketones with Minimally Polarized Alkenes

**Authors:** Yihong Wang, Fenglin Hong, Craig M. Robertson, Richard J. Mudd, John F. Bower

PMC · DOI: 10.1021/jacs.5c19724 · Journal of the American Chemical Society · 2026-01-20

## TL;DR

This paper describes a new iridium-catalyzed method for selectively adding alkenes to α-hydroxy ketones, creating complex cyclic structures with high stereocontrol.

## Contribution

A novel enantio- and diastereoselective iridium-catalyzed α-alkylation method using minimally polarized alkenes.

## Key findings

- Cationic Ir(I)-complexes with homochiral diphosphines enable α-C-H addition to α-hydroxy ketones.
- Intramolecular reactions yield carbocycles with two new stereocenters in a stereocontrolled manner.
- The method represents rare enantioselective Conia-ene-type reactions using alkenes.

## Abstract

Cationic Ir­(I)-complexes modified with homochiral diphosphines
promote the α-C-H addition of α-hydroxy ketones to styrenes
or alkyl olefins. These processes are predicated on the hydroxyl-directed
formation of an Ir-enolate. Inter- and intramolecular processes are
feasible, with the latter offering stereocontrolled access to carbocycles
bearing two new stereocenters. The intramolecular processes constitute
rare examples of alkene-based Conia-ene reactions that are enantio-
and diastereoselective.

## Linked entities

- **Chemicals:** Iridium (PubChem CID 23924)

## Full-text entities

- **Chemicals:** C (MESH:D002244), deuterium (MESH:D003903), Alkenes (MESH:D000475), methyl ketones (MESH:D000096), Ir (MESH:D007495), O-H (MESH:C031356), styrenes (MESH:D013343), BINAP (MESH:C406943), dioxane (MESH:C025223), aldehydes (MESH:D000447), alcohol (MESH:D000438), phenyl ketone (MESH:C047723), 1,2-dichlorobenzene (MESH:C004726), ether (MESH:D004986), alkynes (MESH:D000480), Ru (MESH:D012428), amino acid (MESH:D000596), pi- (MESH:D010716), Os (MESH:D009992), (R)-DM-SynPhos (-), aniline (MESH:C023650), ketone (MESH:D007659)

## Full text

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## Figures

7 figures with captions in the complete paper: https://tomesphere.com/paper/PMC12879937/full.md

## References

18 references — full list in the complete paper: https://tomesphere.com/paper/PMC12879937/full.md

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Source: https://tomesphere.com/paper/PMC12879937