Ni/Photoredox-Catalyzed C(sp 3 )-C(sp 3 ) Coupling between Aziridines and Acetals as Alcohol-Derived Alkyl Radical Precursors.

Item request has been placed! ×
Item request cannot be made. ×
loading   Processing Request
Read More Add to Saved list
  • Author(s): Dongbang S;Dongbang S; Doyle AG; Doyle AG; Doyle AG
  • Source:
    Journal of the American Chemical Society [J Am Chem Soc] 2022 Nov 02; Vol. 144 (43), pp. 20067-20077. Date of Electronic Publication: 2022 Oct 18.
  • Publication Type:
    Journal Article; Research Support, U.S. Gov't, Non-P.H.S.; Research Support, N.I.H., Extramural
  • Language:
    English
  • Additional Information
    • Source:
      Publisher: American Chemical Society Country of Publication: United States NLM ID: 7503056 Publication Model: Print-Electronic Cited Medium: Internet ISSN: 1520-5126 (Electronic) Linking ISSN: 00027863 NLM ISO Abbreviation: J Am Chem Soc Subsets: MEDLINE
    • Publication Information:
      Publication: Washington, DC : American Chemical Society
      Original Publication: Easton, Pa. [etc.]
    • Subject Terms:
      Acetals* ; Aziridines*; Catalysis ; Benzaldehydes ; Nickel
    • Abstract:
      Aziridines are readily available C(sp 3 ) precursors that afford valuable β-functionalized amines upon ring opening. In this article, we report a Ni/photoredox methodology for C(sp 3 )-C(sp 3 ) cross-coupling between aziridines and methyl/1°/2° aliphatic alcohols activated as benzaldehyde dialkyl acetals. Orthogonal activation modes of each alkyl coupling partner facilitate cross-selectivity in the C(sp 3 )-C(sp 3 ) bond-forming reaction: the benzaldehyde dialkyl acetal is activated via hydrogen atom abstraction and β-scission via a bromine radical (generated in situ from single-electron oxidation of bromide), whereas the aziridine is activated at the Ni center via reduction. We demonstrate that an Ni(II) azametallacycle, conventionally proposed in aziridine cross-coupling, is not an intermediate in the productive cross-coupling. Rather, stoichiometric organometallic and linear free energy relationship studies indicate that aziridine activation proceeds via Ni(I) oxidative addition, a previously unexplored elementary step.
    • References:
      Angew Chem Int Ed Engl. 2012 Aug 20;51(34):8573-6. (PMID: 22807193)
      Nature. 2017 May 3;545(7652):84-88. (PMID: 28470192)
      Org Lett. 2018 Jan 19;20(2):421-424. (PMID: 29314848)
      J Am Chem Soc. 2020 May 13;142(19):8928-8937. (PMID: 32348673)
      Chem Sci. 2020 Apr 1;11(16):4051-4064. (PMID: 32864080)
      J Am Chem Soc. 2019 Jul 31;141(30):11821-11826. (PMID: 31310710)
      ACS Chem Neurosci. 2020 Jun 17;11(12):1740-1755. (PMID: 32436697)
      Org Lett. 2021 May 7;23(9):3696-3700. (PMID: 33825468)
      Bioorg Med Chem Lett. 2019 Aug 15;29(16):2042-2050. (PMID: 31272793)
      Eur J Med Chem. 2019 Jan 15;162:679-734. (PMID: 30496988)
      J Org Chem. 1996 Mar 8;61(5):1748-1755. (PMID: 11667045)
      Bioorg Med Chem Lett. 2001 Jan 22;11(2):265-70. (PMID: 11206474)
      J Am Chem Soc. 2015 Sep 16;137(36):11562-5. (PMID: 26325479)
      J Am Chem Soc. 2022 Apr 13;144(14):6185-6192. (PMID: 35353531)
      Org Lett. 2014 Nov 7;16(21):5620-3. (PMID: 25333482)
      J Am Chem Soc. 2015 Aug 26;137(33):10480-3. (PMID: 26256474)
      Chem Rev. 2011 Sep 14;111(9):5215-46. (PMID: 21631125)
      Angew Chem Int Ed Engl. 2018 Apr 3;57(15):4058-4062. (PMID: 29460343)
      Chem Commun (Camb). 2010 Aug 21;46(31):5743-5. (PMID: 20582373)
      J Am Chem Soc. 2022 Jan 19;144(2):1045-1055. (PMID: 34985904)
      Bioorg Med Chem Lett. 2005 Feb 15;15(4):977-82. (PMID: 15686896)
      J Am Chem Soc. 2014 Jun 18;136(24):8544-7. (PMID: 24870625)
      Org Lett. 2004 Oct 28;6(22):4109-12. (PMID: 15496111)
      Org Lett. 2021 Jul 16;23(14):5471-5475. (PMID: 34197130)
      Chem Sci. 2018 Nov 9;10(4):1144-1149. (PMID: 30774912)
      J Am Chem Soc. 2002 Mar 27;124(12):2890-1. (PMID: 11902877)
      Top Curr Chem (Cham). 2016 Aug;374(4):43. (PMID: 27573395)
      Chemistry. 2011 Jan 3;17(1):286-96. (PMID: 21207624)
      ACS Med Chem Lett. 2012 Mar 02;3(4):332-6. (PMID: 24900473)
      J Am Chem Soc. 2021 Sep 8;143(35):14196-14206. (PMID: 34432468)
      Chem Commun (Camb). 2018 Jun 8;54(47):6024-6027. (PMID: 29796543)
      Webmedcentral. 2013 Sep 30;4(9):. (PMID: 24482732)
      J Am Chem Soc. 2020 Dec 9;142(49):20594-20599. (PMID: 33252234)
      J Am Chem Soc. 2017 Apr 26;139(16):5688-5691. (PMID: 28406622)
      Bioorg Med Chem. 2007 Dec 15;15(24):7677-87. (PMID: 17869522)
      J Org Chem. 2014 Jun 6;79(11):4793-8. (PMID: 24820397)
      Inorg Chem. 2011 Nov 21;50(22):11514-26. (PMID: 21961698)
      J Am Chem Soc. 2019 Nov 6;141(44):17937-17948. (PMID: 31589820)
      J Med Chem. 2010 Mar 25;53(6):2443-63. (PMID: 20163176)
      Chem Sci. 2020 Sep 9;11(38):10461-10464. (PMID: 34094304)
      Chemistry. 2019 Aug 1;25(43):10226-10231. (PMID: 31161639)
      J Med Chem. 2008 Jan 24;51(2):305-13. (PMID: 18095642)
      Chemistry. 2010 May 25;16(20):5848-52. (PMID: 20379979)
      J Am Chem Soc. 2012 Oct 17;134(41):17003-6. (PMID: 23039358)
      J Am Chem Soc. 2013 Sep 11;135(36):13605-9. (PMID: 23961769)
      Nature. 2022 Jun;606(7913):313-318. (PMID: 35381598)
      J Am Chem Soc. 2020 Jun 24;142(25):10936-10941. (PMID: 32520556)
      J Am Chem Soc. 2019 Jun 5;141(22):8914-8920. (PMID: 31136162)
      J Am Chem Soc. 2012 Jun 13;134(23):9541-4. (PMID: 22414150)
      Angew Chem Int Ed Engl. 2013 Nov 18;52(47):12256-67. (PMID: 24151256)
      Org Lett. 2022 Apr 22;24(15):2853-2857. (PMID: 35416673)
      Org Lett. 2021 Oct 1;23(19):7364-7369. (PMID: 34543571)
      J Am Chem Soc. 2014 Aug 6;136(31):11145-52. (PMID: 25055180)
      J Am Chem Soc. 2017 Oct 4;139(39):13929-13935. (PMID: 28880544)
      J Am Chem Soc. 2015 May 6;137(17):5638-41. (PMID: 25879801)
      J Am Chem Soc. 2020 Apr 22;142(16):7683-7689. (PMID: 32275411)
      J Am Chem Soc. 2013 Dec 11;135(49):18347-9. (PMID: 24298978)
      Bioorg Med Chem Lett. 1999 Jul 19;9(14):1915-20. (PMID: 10450953)
      Bioorg Med Chem Lett. 2001 Jan 22;11(2):259-64. (PMID: 11206473)
      J Med Chem. 2015 Oct 8;58(19):7749-62. (PMID: 26393416)
      J Am Chem Soc. 2010 Jan 27;132(3):920-1. (PMID: 20047282)
      Chemistry. 2014 Nov 17;20(47):15334-8. (PMID: 25308802)
      J Am Chem Soc. 2020 Apr 22;142(16):7598-7605. (PMID: 32250602)
      J Org Chem. 2013 Nov 1;78(21):10960-7. (PMID: 24087851)
      J Med Chem. 2000 Nov 16;43(23):4354-8. (PMID: 11087558)
      J Am Chem Soc. 2022 Jan 26;144(3):1113-1118. (PMID: 35029387)
      Nature. 2016 Aug 17;536(7616):322-5. (PMID: 27535536)
      Org Lett. 2018 Jun 15;20(12):3618-3621. (PMID: 29874082)
      Chemistry. 2013 Aug 12;19(33):10840-4. (PMID: 23818425)
      J Am Chem Soc. 2021 Apr 7;143(13):4949-4954. (PMID: 33724815)
      J Am Chem Soc. 2016 Jul 6;138(26):8084-7. (PMID: 27263662)
      J Am Chem Soc. 2021 Sep 29;143(38):15873-15881. (PMID: 34542286)
      Bioorg Med Chem Lett. 2011 Mar 1;21(5):1394-8. (PMID: 21292480)
      Org Lett. 2011 Apr 15;13(8):2138-41. (PMID: 21434609)
      Org Lett. 2017 Apr 7;19(7):1738-1740. (PMID: 28296408)
      Chem Rev. 2022 Jan 26;122(2):1485-1542. (PMID: 34793128)
      Org Lett. 2018 Apr 6;20(7):1880-1883. (PMID: 29561162)
      Chem Sci. 2019 Jul 31;10(37):8642-8647. (PMID: 31803438)
      J Am Chem Soc. 2018 Apr 11;140(14):4792-4796. (PMID: 29584958)
      Organometallics. 2020 Apr 27;39(8):1139-1144. (PMID: 32362705)
      Nature. 2022 Apr;604(7905):292-297. (PMID: 35189623)
      Org Lett. 2017 Mar 3;19(5):1076-1079. (PMID: 28230379)
      J Am Chem Soc. 2014 Oct 15;136(41):14365-8. (PMID: 25245492)
      Acc Chem Res. 2015 Jun 16;48(6):1767-75. (PMID: 26011466)
      Science. 2021 Dec 03;374(6572):1258-1263. (PMID: 34762491)
    • Grant Information:
      R35 GM126986 United States GM NIGMS NIH HHS
    • Accession Number:
      0 (Acetals)
      TA269SD04T (benzaldehyde)
      0 (Benzaldehydes)
      7OV03QG267 (Nickel)
      0 (Aziridines)
    • Publication Date:
      Date Created: 20221018 Date Completed: 20221103 Latest Revision: 20230621
    • Publication Date:
      20230621
    • Accession Number:
      PMC10281197
    • Accession Number:
      10.1021/jacs.2c09294
    • Accession Number:
      36256882