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. 2024 Jul 10;146(27):18224-18229.
doi: 10.1021/jacs.4c06601. Epub 2024 Jun 25.

Directed Hydrogen Atom Transfer for Selective Reactions of Polyenols

Daniel E Essayan  1 , Matthew J Schubach  1 , Jeanelle M Smoot  1 , Taranee Puri  1 , Sergey V Pronin  1
Affiliations

Directed Hydrogen Atom Transfer for Selective Reactions of Polyenols

Daniel E Essayan et al. J Am Chem Soc. .

Abstract

Directed hydrogen atom transfer to alkenes is described. The process is catalyzed by iron complexes and allows for the site-selective hydrofunctionalization of polyenols. Experimental data suggest that coordination of the hydroxy group to the iron hydride intermediate plays an important role in preferential engagement of the allylic alcohol motif and provides a new basis for selectivity in radical hydrofunctionalization events. As a proof of concept, β- and γ-amino alcohols are prepared from the corresponding polyenols in a selective manner.

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Figures

Figure 1.
Figure 1.
Directed HAT allows for the selective engagement of allylic alcohol motifs.
Scheme 1.
Scheme 1.
Proposed Mechanism of the Directed HAT
Scheme 2.
Scheme 2.. Stereochemical Outcome of the Directed HATa
aBased on 1H NMR analysis.
See this image and copyright information in PMC

References

    1. For pioneering examples of relevant reactivity, see: Mukaiyama T; Yamada T Recent advances in aerobic oxygenation. Bull. Chem. Soc. Jpn 1995, 68, 17 and references therein.
    1. For early examples of relevant mechanistic considerations, see: Eisenberg DC; Norton JR Hydrogen-atom transfer reactions of transition-metal hydrides. Isr. J. Chem 1991, 31, 55.
    2. Ishikawa H; Colby DA; Seto S; Va P; Tam A; Kakei H; Rayl TJ; Hwang I; Boger DL Total synthesis of vinblastine, vincristine, related natural products, and key structural analogues. J. Am. Chem. Soc 2009, 131, 4904. - PMC - PubMed
    3. Iwasaki K; Wan KK; Oppedisano A; Crossley SWM; Shenvi RA Simple, chemoselective hydrogenation with thermodynamic control. J. Am. Chem. Soc 2014, 136, 1300. - PMC - PubMed
    4. King SM; Ma X; Herzon SB A method for the selective hydrogenation of alkenyl halides to alkyl halides. J. Am. Chem. Soc 2014, 136, 6884. - PubMed
    1. For an excellent review, see: Crossley SWM; Martinez RM; Obradors C; Shenvi RA Mn, Fe, and Co-catalyzed radical hydrofunctionalizations of olefins. Chem. Rev 2016, 116, 8912. - PMC - PubMed
    1. For a discussion of mechanistic underpinnings, see: Shevick SL; Wilson CV; Kotesova S; Kim D; Holland PL; Shenvi RA Catalytic hydrogen atom transfer to alkenes: a roadmap for metal hydrides and radicals. Chem. Sci 2020, 11, 12401. - PMC - PubMed
    1. For relevant examples of selective reactions, see: Magnus P; Payne AH; Waring MJ; Scott DA; Lynch V Conversion of α,β-unsaturated ketones into α-hydroxyketones using an MnIII catalyst, phenylsilane and dioxygen: acceleration of conjugate hydride reduction by dioxygen. Tetrahedron Lett. 2000, 41, 9725.
    2. Waser J; González-Gómez JC; Nambu H; Huber P; Carreira EM Cobalt-catalyzed hydrohydrazination of dienes and enynes: access to allylic and propargylic hydrazides. Org. Lett 2005, 7, 4249. - PubMed
    3. Taniguchi T; Goto N; Nishibata A; Ishibashi H Iron-catalyzed redox radical cyclizations of 1,6-dienes and enynes. Org. Lett 2010, 12, 112. - PubMed
    4. Leggans EK; Barker TJ; Duncan KK; Boger DL Iron(III)/NaBH4-mediated additions to unactivated alkenes: synthesis of novel 20′-vinblastine analogues. Org. Lett 2012, 14, 1428. - PMC - PubMed
    5. Vrubliauskas D; Vanderwal CD Cobalt-catalyzed hydrogen atom transfer induces bicyclizations that tolerate electron-rich and electron-deficient intermediate alkenes. Angew. Chem., Int. Ed 2020, 59, 6115. - PMC - PubMed
    6. Mondal B; Hazra S; Chatterjee A; Patel M; Saha J Fe-catalyzed hydroallylation of unactivated alkenes with vinyl cyclopropanes. Org. Lett 2023, 25, 5676. - PubMed

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