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The Tishchenko Reaction

In this Named Reaction episode, we explore the Tishchenko reaction and related transformations. This episode has an associated problem set available to download on synthesis-workshop.com. References (in order of appearance): Seminal work on the Tishchenko reaction: (a) Ber. 1887, 20, 646. (b) J. Russ. Phys. Chem. Soc. 1906, 38, 355. (c) Chem. Zentr. 1906, II, 1309-1311. (d) Chem. Zentr. 1906, II, 1552-1555. (e) Chem. Zentr. 1906, II, 155-1556. For an early mechanistic discussion, see: J. Am. Chem. Soc. 1952, 74, 5133-5135. Variants with divalent or trivalent Sm have been reported: (a) J. Org. Chem. 1999, 64, 843-853. (b) J. Org. Chem. 2001, 66, 8573-8584. X is sometimes left unspecified in literature and other times is replaced with two iodine ligands. For foundational work on the Evans-Tishchenko reaction, see: J. Am. Chem. Soc. 1990, 112, 6447-6449. J. Am. Chem. Soc. 2004, 126, 7782-7783. For a pioneering example, see: Angew. Chem. Int. Ed. 2001, 40, 601-603. For a review on developments in the asymmetric aldol-Tishchenko reaction, see: Eur. J. Org. Chem. 2006, 2006, 4779-4786. Org. Lett. 2015, 17, 5642-5645. For more on the Ellman auxiliary, see: Chem. Rev. 2010, 110, 3600-3740. For other recent developments, see: (a) J. Org. Chem. 2021, 86, 4296-4303. (b) Org. Lett. 2021, 23, 6372-6376. For more on samarium promoted aldol reactions and aldol-Tishchenko: (a) J. Org. Chem. 1999, 64, 843-853. (b) J. Org. Chem. 2001, 66, 8573-8584. b-hydroxyketone intermediate may also be drawn as an alkoxide. For another example of using SmI2 to utilize a-bromoketones in Reformatsky-type reactions, see: (a) J. Am. Chem. Soc. 2006, 128, 15106-15107. (b) J. Org. Chem. 2007, 72, 9736-9745. Org. Lett. 2019, 21, 5471-5474. For more on the synthesis of this starting material, see: Org. Lett. 2011, 13, 2506-2509. Angew. Chem. Int. Ed. 2018, 57, 5143-5146. Also see work on this target using the Narasaka-Prasad reduction: (a) J. Am. Chem. Soc. 2010, 132, 10286-10292. (b) J. Am. Chem. Soc. 2015, 137, 15426-15429. For further developments, see: Chem. Asian J. 2020, 15, 3494-3502. Also see work on this target using the Narasaka-Prasad reduction: (a) J. Am. Chem. Soc. 2010, 132, 10286-10292. (b) J. Am. Chem. Soc. 2015, 137, 15426-15429. J. Am. Chem. Soc. 2015, 137, 15426-15429. For more on this dithiane deprotection, see: Tetrahedron Lett. 2013, 54, 5477-5480. For more on the Narasaka-Prasad reduction, see: Tetrahedron 1984, 40, 2233-2238. For a foundational application of the Narasaka-Prasad reduction in this system, see: J. Am. Chem. Soc. 2010, 132, 10286-10292. Science 2017, 358, 218-223. For original reports of Evans-Saksena Reduction, see a) Tetrahedron Lett. 1983, 24, 273-276; b) J. Am. Chem. Soc. 1988, 110, 3560-3578. Org. Biomol. Chem. 2011, 9, 984-986. Also see the work of Kim and Hong on this target: Org. Lett. 2010, 12, 2880-2883. J. Am. Chem. Soc. 2003, 125, 350-351. For prior work on this type of Evans-Tishchenko reaction, see: Org. Lett. 2002, 4, 4539-4541. Related applications: (a) Proc. Natl. Acad. Sci. U.S.A. 2004, 101, 12042-12047. (b) J. Am. Chem. Soc. 2007, 129, 10957-10962.