Synthesis Workshop: Rearrangements of Indole-based Onium-Ylides with Vaishnavi Nair (Episode 58)

In this Research Spotlight episode, Vaishnavi Nair (Tambar lab, UT Southwestern Medical Center) joins to share her work on catalyst-controlled regiodivergence in rearrangements of indole-based onium-ylides.

Key reference: J. Am. Chem. Soc. 2021, 143, 9016-9025.

Additional references (in order of appearance):
Review on onium-ylide rearrangements: Sweeney, Chem. Soc. Rev. 2009, 38, 1027-1038.
J. Am. Chem. Soc. 2016, 138, 12073-12076.
Reviews on catalytic onium-ylide rearrangements: (a) Chem. Soc. Rev. 2001, 30, 50−61. (b) ACS Catal. 2015, 5, 7446−7479.
For literature examples see: Chem. Commun. 2017, 53, 6219-6222. Chem. Commun. 2019, 55, 8410-8413.
Examples of [1,2]-rearrangement of cyclic oxonium ylides: (a) J. Org. Chem. 1994, 59, 6892−6894. (b) Tetrahedron Lett. 1993, 34, 4385−4388.
For reactions of indoles with metal carbenoids, see: Adv. Heterocycl. Chem. 2013, 110, 43-72.
Examples of dissociation of rhodium to give free ylide: J. Org. Chem. 1981, 46, 5094−5102. ACS Catal. 2021, 11, 829−839.
Isolation Paper: J. Nat. Prod. 2016, 79, 369-375.