Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2019 Nov 11;58(46):16490-16494.
doi: 10.1002/anie.201909426. Epub 2019 Sep 26.

Combined Photoredox/Enzymatic C-H Benzylic Hydroxylations

Rick C Betori  1 , Catherine M May  1 , Karl A Scheidt  1
Affiliations

Combined Photoredox/Enzymatic C-H Benzylic Hydroxylations

Rick C Betori et al. Angew Chem Int Ed Engl. .

Retraction in

Abstract

Chemical transformations that install heteroatoms into C-H bonds are of significant interest because they streamline the construction of value-added small molecules. Direct C-H oxyfunctionalization, or the one step conversion of a C-H bond to a C-O bond, could be a highly enabling transformation due to the prevalence of the resulting enantioenriched alcohols in pharmaceuticals and natural products,. Here we report a single-flask photoredox/enzymatic process for direct C-H hydroxylation that proceeds with broad reactivity, chemoselectivity and enantioselectivity. This unified strategy advances general photoredox and enzymatic catalysis synergy and enables chemoenzymatic processes for powerful and selective oxidative transformations.

Keywords: C−H oxidation; chemoenzymatic catalysis; chiral alcohols; ketoreductase; photoredox catalysis.

PubMed Disclaimer

Figures

Figure 1.
Figure 1.
Approaches to Benzylic C–H Hydroxylation
Figure 2.
Figure 2.
Optimization of Reaction Conditions
Figure 3.
Figure 3.
Site-Selectivity Studies
Figure 4.
Figure 4.
Mechanistic Studies
See this image and copyright information in PMC

References

    1. Davies HML, Manning JR, Nature 2008, 451, 417; - PMC - PubMed
    2. Yi H, Zhang G, Wang H, Huang Z, Wang J, Singh AK, Lei A, Chem. Rev. 2017, 117, 9016–9085; - PubMed
    3. Zhang X, Rakesh KP, Ravindar L, Qin H-L, Green Chem. 2018, 20, 4790–4833.
    1. Kille S, Zilly FE, Acevedo JP, Reetz MT, Nat. Chem. 2011, 3, 738; - PubMed
    2. Kudrik EV, Afanasiev P, Alvarez LX, Dubourdeaux P, Clémancey M, Latour J-M, Blondin G, Bouchu D, Albrieux F, Nefedov SE, Sorokin AB, Nat. Chem. 2012, 4, 1024; - PubMed
    3. Wencel-Delord J, Glorius F, Nat. Chem. 2013, 5, 369; - PubMed
    4. Zhang W, Wang F, McCann SD, Wang D, Chen P, Stahl SS, Liu G, Science 2016, 353, 1014; - PMC - PubMed
    5. Zhang W, Fernández-Fueyo E, Ni Y, van Schie M, Gacs J, Renirie R, Wever R, Mutti FG, Rother D, Alcalde M, Hollmann F, Nat. Catal. 2018, 1, 55–62. - PMC - PubMed
    1. Devine PN, Howard RM, Kumar R, Thompson MP, Truppo MD, Turner NJ, Nat. Rev. Chem. 2018, 2, 409–421;
    2. van Sch MMCH, Zhang W, Tieves F, Choi DS, Park CB, Burek BO, Bloh JZ, Arends IWCE, Paul CE, Alcalde M, Hollmann F, ACS. Catal. 2019, 10.1021/acscatal.9b01341,7409-7417. - DOI
    1. Choudary BM, Prasad AD, Bhuma V, Swapna V, J. Org. Chem. 1992, 57, 5841–5844;
    2. Shaabani A, Lee DG, Tetrahedron Lett. 2001, 42, 5833–5836;
    3. Shaabani A, Mirzaei P, Naderi S, Lee DG, Tetrahedron 2004, 60, 11415–11420.
    1. Baran PS, Zhong Y-L, J. Am. Chem. Soc. 2001, 123, 3183–3185; - PubMed
    2. Lee JM, Park EJ, Cho SH, Chang S, J. Am. Chem. Soc. 2008, 130, 7824–7825; - PubMed
    3. Chen MS, White MC, Science 2010, 327, 566; - PubMed
    4. Xia J-B, Cormier KW, Chen C, Chem. Sci. 2012, 3, 2240–2245; - PMC - PubMed
    5. Howell JM, Feng K, Clark JR, Trzepkowski LJ, White MC, J. Am. Chem. Soc. 2015, 137, 14590–14593; - PMC - PubMed
    6. Gensch T, Hopkinson MN, Glorius F, Wencel-Delord J, Chem. Soc. Rev. 2016, 45, 2900–2936; - PubMed
    7. Gini A, Brandhofer T, Mancheno OG, Org. Biomol. Chem. 2017, 15, 1294–1312; - PubMed
    8. Nanjo T, de Lucca EC, White MC, J. Am. Chem. Soc. 2017, 139, 14586–14591; - PMC - PubMed
    9. Li G-X, Morales-Rivera CA, Gao F, Wang Y, He G, Liu P, Chen G, Chem. Sci. 2017, 8, 7180–7185; - PMC - PubMed
    10. White MC, Zhao J, J. Am. Chem. Soc. 2018, 140, 13988–14009. - PMC - PubMed

Publication types

LinkOut - more resources