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Photomechanical actuation of ligand geometry in enantioselective catalysis.

Publication ,  Journal Article
Kean, ZS; Akbulatov, S; Tian, Y; Widenhoefer, RA; Boulatov, R; Craig, SL
Published in: Angewandte Chemie (International ed. in English)
December 2014

A catalyst that couples a photoswitch to the biaryl backbone of a chiral bis(phosphine) ligand, thus allowing photochemical manipulation of ligand geometry without perturbing the electronic structure is reported. The changes in catalyst activity and selectivity upon switching can be attributed to intramolecular mechanical forces, thus laying the foundation for a new class of catalysts whose selectivity can be varied smoothly and in situ over a useful range by controlling molecular stress experienced by the catalyst during turnover. Forces on the order of 100 pN are generated, thus leading to measurable changes in the enantioselectivities of asymmetric Heck arylations and Trost allylic alkylations. The differential coupling between applied force and competing stereochemical pathways is quantified and found to be more efficient for the Heck arylations.

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Published In

Angewandte Chemie (International ed. in English)

DOI

EISSN

1521-3773

ISSN

1433-7851

Publication Date

December 2014

Volume

53

Issue

52

Start / End Page

14508 / 14511

Related Subject Headings

  • Organic Chemistry
  • 34 Chemical sciences
  • 03 Chemical Sciences
 

Citation

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Kean, Z. S., Akbulatov, S., Tian, Y., Widenhoefer, R. A., Boulatov, R., & Craig, S. L. (2014). Photomechanical actuation of ligand geometry in enantioselective catalysis. Angewandte Chemie (International Ed. in English), 53(52), 14508–14511. https://doi.org/10.1002/anie.201407494
Kean, Zachary S., Sergey Akbulatov, Yancong Tian, Ross A. Widenhoefer, Roman Boulatov, and Stephen L. Craig. “Photomechanical actuation of ligand geometry in enantioselective catalysis.Angewandte Chemie (International Ed. in English) 53, no. 52 (December 2014): 14508–11. https://doi.org/10.1002/anie.201407494.
Kean ZS, Akbulatov S, Tian Y, Widenhoefer RA, Boulatov R, Craig SL. Photomechanical actuation of ligand geometry in enantioselective catalysis. Angewandte Chemie (International ed in English). 2014 Dec;53(52):14508–11.
Kean, Zachary S., et al. “Photomechanical actuation of ligand geometry in enantioselective catalysis.Angewandte Chemie (International Ed. in English), vol. 53, no. 52, Dec. 2014, pp. 14508–11. Epmc, doi:10.1002/anie.201407494.
Kean ZS, Akbulatov S, Tian Y, Widenhoefer RA, Boulatov R, Craig SL. Photomechanical actuation of ligand geometry in enantioselective catalysis. Angewandte Chemie (International ed in English). 2014 Dec;53(52):14508–14511.
Journal cover image

Published In

Angewandte Chemie (International ed. in English)

DOI

EISSN

1521-3773

ISSN

1433-7851

Publication Date

December 2014

Volume

53

Issue

52

Start / End Page

14508 / 14511

Related Subject Headings

  • Organic Chemistry
  • 34 Chemical sciences
  • 03 Chemical Sciences