PMID- 36787801
OWN - NLM
STAT- PubMed-not-MEDLINE
DCOM- 20230407
LR  - 20240402
IS  - 1476-4687 (Electronic)
IS  - 0028-0836 (Print)
IS  - 0028-0836 (Linking)
VI  - 616
IP  - 7955
DP  - 2023 Apr
TI  - Enantioselective transition-metal catalysis via an anion-binding approach.
PG  - 84-89
LID - 10.1038/s41586-023-05804-3 [doi]
AB  - Asymmetric transition-metal catalysis represents a powerful strategy for 
      accessing enantiomerically enriched molecules(1-3). The classical strategy for 
      inducing enantioselectivity with transition-metal catalysts relies on direct 
      complexation of chiral ligands to produce a sterically constrained reactive metal 
      site that allows formation of the major product enantiomer while effectively 
      inhibiting the pathway to the minor enantiomer through steric repulsion(4). The 
      chiral-ligand strategy has proven applicable to a wide variety of highly 
      enantioselective transition-metal-catalysed reactions, but important scenarios 
      exist that impose limits to its successful adaptation. Here, we report a new 
      approach for inducing enantioselectivity in transition-metal-catalysed reactions 
      that relies on neutral hydrogen-bond donors (HBDs)(5,6) that bind anions of 
      cationic transition-metal complexes to achieve enantiocontrol and rate 
      enhancement through ion pairing together with other non-covalent 
      interactions(7-9). A cooperative anion-binding effect of a chiral bis-thiourea 
      HBD is demonstrated to lead to high enantioselectivity (up to 99% enantiomeric 
      excess) in intramolecular ruthenium-catalysed propargylic substitution 
      reactions(10). Experimental and computational mechanistic studies show the 
      attractive interactions between electron-deficient arene components of the HBD 
      and the metal complex that underlie enantioinduction and the acceleration effect.
CI  - (c) 2023. The Author(s), under exclusive licence to Springer Nature Limited.
FAU - Ovian, John M
AU  - Ovian JM
AUID- ORCID: 0000-0001-5362-5010
AD  - Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA, 
      USA.
FAU - Vojackova, Petra
AU  - Vojackova P
AUID- ORCID: 0000-0002-7543-9355
AD  - Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA, 
      USA.
FAU - Jacobsen, Eric N
AU  - Jacobsen EN
AUID- ORCID: 0000-0001-7952-3661
AD  - Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA, 
      USA. jacobsen@chemistry.harvard.edu.
LA  - eng
GR  - R01 GM043214/GM/NIGMS NIH HHS/United States
GR  - R37 GM043214/GM/NIGMS NIH HHS/United States
PT  - Journal Article
PT  - Research Support, N.I.H., Extramural
PT  - Research Support, Non-U.S. Gov't
PT  - Research Support, U.S. Gov't, Non-P.H.S.
DEP - 20230214
PL  - England
TA  - Nature
JT  - Nature
JID - 0410462
SB  - IM
PMC - PMC10388379
MID - NIHMS1920686
COIS- Competing Interests: The authors declare no competing interests.
EDAT- 2023/02/15 06:00
MHDA- 2023/04/07 06:41
PMCR- 2024/04/01
CRDT- 2023/02/14 19:13
PHST- 2022/08/25 00:00 [received]
PHST- 2023/02/06 00:00 [accepted]
PHST- 2023/04/07 06:41 [medline]
PHST- 2023/02/15 06:00 [pubmed]
PHST- 2023/02/14 19:13 [entrez]
PHST- 2024/04/01 00:00 [pmc-release]
AID - 10.1038/s41586-023-05804-3 [pii]
AID - 10.1038/s41586-023-05804-3 [doi]
PST - ppublish
SO  - Nature. 2023 Apr;616(7955):84-89. doi: 10.1038/s41586-023-05804-3. Epub 2023 Feb 
      14.