Advanced Organic Chemistry: Asymmetric Epoxidation

In this installment of the Synthesis Workshop Advanced Organic Chemistry Course, Dr. Matthew Horwitz discusses approaches to asymmetric epoxidation.

Link to Julia-Colonna model in Rowan (credit: Corin Wagen):
https://labs.rowansci.com/public/calc...

This episode also has an associated problem set available at https://synthesis-workshop.com/#probl....

References:
Reviews: Chem. Rev. 2008, 108, 3958-3987; Chem. Soc. Rev. 2011, 40, 1722-1760; Chem. Rev. 2014, 114, 8199-8256.
For approaches based on chiral auxiliaries, see: Tetrahedron Lett. 1984, 25, 3273-3276; Tetrahedron Lett. 1991, 32, 2857-2860; Chem. Commun. 2000, 495-496.
For seminal work, see: J. Am. Chem. Soc. 1980, 102, 5974-5976. Also see: Strategic Applications of Named Reactions in Organic Synthesis by Kürti and Czakó (Elsevier, 2005) for more on this reaction and also others in this talk.
For mechanistic work, see: Pure Appl. Chem. 1983, 55, 1823-1836; J. Org. Chem. 1990, 55, 1693-1694; J. Am. Chem. Soc. 1991, 113, 106-113; J. Am. Chem. Soc. 1991, 113, 113-126.
Examples and kinetic resolution: J. Am. Chem. Soc. 1987, 109, 5765-5780. Myers notes on Sharpless Asymmetric Epoxidation Reaction: https://hwpi.harvard.edu/files/myers/...
Org. Lett. 2019, 21, 785-788.
Org. Lett. 2016, 18, 2399-2402.
Amphirionin-4 synthesis: Org. Lett. 2016, 18, 2399-2402. Diastereoselective etherification: Tetrahedron Lett. 1988, 29, 2011-2013.
For seminal work, see: J. Am. Chem. Soc. 1990, 112, 2801-2803; J. Am. Chem. Soc. 1991, 113, 7063-7064; Tetrahedron Lett. 1991, 32, 1055-1058; Tetrahedron: Asymmetry 1991, 2, 481-494.
Angew. Chem. Int. Ed. 1997, 36, 1718-1719; Angew. Chem. Int. Ed. 1997, 36, 2060-2062; J. Org. Chem. 1997, 62, 2222-2229; Org. Lett. 1999, 1, 419-422; J. Am. Chem. Soc. 2005, 127, 13672-13679; Org. Lett. 2009, 11, 4592-4595.
J. Org. Chem. 1994, 59, 4378-4380.
Synthesis 2011, 18, 2929-2934.
Angew. Chem. Int. Ed. 2019, 58, 1427-1431. For prior example of achieving kinetic resolution in a related system for the synthesis of (+)-teretifolione B, see: J. Org. Chem. 1995, 60, 5380-5381.
Key foundational papers: Science 1997, 277, 936-938; J. Am. Chem. Soc. 2002, 124, 1307-131; J. Am. Chem. Soc. 2004, 126, 1360-1362. Synthesis of (2E)-macrolactin 3: Synlett 2023, 34, 67-72.
Chem. Eur. J. 2013, 19, 4532-4537. For more on this sequence, see: Angew. Chem. Int. Ed. 2010, 49, 6147-6150. For the prior report that enabled this formal synthesis, see: J. Am. Chem. Soc. 2010, 132, 4564-4565.
J. Am. Chem. Soc. 1996, 118, 9806-9807; J. Am. Chem. Soc. 1997, 119, 11224-11235; J. Org. Chem. 1997, 62, 2328-2329; J. Am. Chem. Soc. 1998, 120, 5943-5952; J. Am. Chem. Soc. 1999, 121, 7718-7719.
J. Org. Chem. 1998, 63, 2948-2953; J. Am. Chem. Soc. 1997, 119, 11224-11235; Tetrahedron Lett. 1998, 39, 7819-7822; J. Org. Chem. 1999, 64, 7646-7650.
J. Org. Chem. 1997, 62, 2328-2329; Synthesis 2000, 1979-2000.
For initial reports, see: Angew. Chem. Int. Ed. 1980, 19, 929-931; J. Chem. Soc., Perkin Trans. 1 1982, 1317-1324. Also see: Chem. Commun. 2004, 2018-2020; Adv. Synth. Catal. 2004, 346, 1247-1249; Synlett 2002, 5, 707-710.
J. Chem. Soc., Perkin Trans. 1 1997, 3501-3508. For more on I-PLL, see: J. Org. Chem. 1990, 55, 6047-6049. Also see the synthesis of (+)-clausenamide: Chem. Commun. 1998, 1159-1160.
For other approaches by Enders and Corey to the asymmetric epoxidation of enones, see: Angew. Chem. Int. Ed. 1996, 35, 1725-1728; Org. Lett. 1999, 1, 1287-1290.
J. Am. Chem. Soc. 2001, 123, 2725-2732. Also see work of Jackson group, using tartrate-derived magnesium alkoxides with TBHP in asymmetric epoxidations: Chem. Commun. 2001, 2712-2713.
J. Am. Chem. Soc. 2002, 124, 14544-14545.
J. Am. Chem. Soc. 2005, 127, 6964-6965; Org. Biomol. Chem. 2005, 3, 3883-3885; Chem. Eur J. 2014, 20, 64-67.
J. Am. Chem. Soc. 2008, 130, 6070-6071. For subsequent work with branched enals, see: J. Am. Chem. Soc. 2010, 132, 10227-10229. Also see: Tetrahedron 2006, 62, 11413-11424; Angew Chem. Int. Ed. 2008, 47, 1119.
Chem. Sci. 2012, 3, 1996-2000; Adv. Synth. Catal. 2017, 359, 3454-3459; Org. Lett. 2021, 23, 6961-6966.
J. Am. Chem. Soc. 2001, 123, 7194-7195. Also see: Angew. Chem. Int. Ed. 1999, 38, 937-941; Chem. Commun. 2007, 1166-1168; Angew. Chem. Int. Ed. 2007, 46, 7293-7296; Chem. Commun. 2008, 3801-3803.
J. Am. Chem. Soc. 2011, 133, 8432-8435. For subsequent asymmetric epoxidation work by Yamamoto in a bimetallic system, see: J. Am. Chem. Soc. 2015, 137, 15612-15615.
Also see the Yamamoto group’s work on vanadium-catalyzed and tungsten-catalyzed asymmetric epoxidation of homoallylic alcohols: J. Am. Chem. Soc. 2007, 129, 286-287; J. Am. Chem. Soc. 2014, 136, 1222-1225.
J. Am. Chem. Soc. 2016, 138, 2732-2738.
Also see: Asymmetric Darzens reaction – review: ChemCatChem, 2018, 10, 5092-5114.