This document presents 5 problems involving the synthesis and reaction mechanisms of arynes. The problems involve transformations reported by different research groups utilizing aryne precursors and various reaction conditions. Students are tasked with identifying products and proposing plausible mechanisms for the reactions based on the information provided.
This document presents 5 problems involving the synthesis and reaction mechanisms of arynes. The problems involve transformations reported by different research groups utilizing aryne precursors and various reaction conditions. Students are tasked with identifying products and proposing plausible mechanisms for the reactions based on the information provided.
This document presents 5 problems involving the synthesis and reaction mechanisms of arynes. The problems involve transformations reported by different research groups utilizing aryne precursors and various reaction conditions. Students are tasked with identifying products and proposing plausible mechanisms for the reactions based on the information provided.
This document presents 5 problems involving the synthesis and reaction mechanisms of arynes. The problems involve transformations reported by different research groups utilizing aryne precursors and various reaction conditions. Students are tasked with identifying products and proposing plausible mechanisms for the reactions based on the information provided.
1. Propose and explain a plausible mechanism for the following transformation reported by Glorius and co-workers. (ACIE 2010, 49, 9761–9764). [★]
NHC (15 mol%)
O O TMS KOtBu (15 mol%) H + N ClO4– R TfO KF (2.0 equiv.) R S [18]crown-6 (2.0 equiv.) (1.1 equiv.) THF, 25 ºC, 4 h NHC
2. In 2020, Wei and co-coworkers reported the following Pd-catalyzed transformation (Org. Lett. 2020, 22, 7470-7474). Identifying the product and propose a plausible mechanism. [★★]
Pd(OAc)2 (10 mol%)
CuO (2.0 equiv.) O TMS CsOAc (1.0 equiv.) R’ S NH + R TfO CsF (4.0 equiv.) (2.0 equiv.) 1-AdCO2H (1.0 equiv.) 1,4-dioxane, 110 ºC, 24 h
3. Identifying the product and propose a plausible mechanism for the following transformation reported by Biju and co- workers (Chem. Commun. 2019, 55, 3004-3007). [★★]
KF (3.0 equiv.) N TMS [18]crown-6 (3.0 equiv.) + R MeO2C CO2tBu TfO THF, -10 ºC to RT, 17 h (1.5 equiv.)
4. Propose the structure of the product formed in this transformation reported by Sing and co-workers (J. Org. Chem. 2022, 87, 7219-7228). Justify your answer with a plausible mechanism. [★★★]
Ar TMS CsF (4.0 equiv.)
O OEt + N TfO MeCN under N2, 70 ºC, 3 h
(3.0 equiv.)
5. In 2022, Arun and co-workers reported the following transformation (J. Org. Chem. 2021, 23, 6372-6376). Identifying the missing starting materials and propose a plausible mechanism. [★★]
Ca(NTf2)2 (2 mol%) R MeO OMe TMS CsF (3.0 equiv.) + + + Ar TfO MeCN, RT, 7-12 h N OMe R’ (1.05 equiv.) then 1% HCl aq. (1.05 equiv.) (1.5 equiv.)
