The Synthesis and Base-Induced Breakdown of Triaryl 1,4-Oxathiins—An Experimental and DFT Study
Abstract
:1. Introduction
2. Results and Discussion
2.1. Preparation of Substituted 1,4-Oxathiins
2.2. Computational Chemistry
2.2.1. Oxathiin Ring Formation
2.2.2. Oxathiin Ring Opening
2.2.3. Proton Transfer Options and Overall Pathway
3. Experimental
3.1. General Reaction Procedures
3.2. Preparation of Trisubstituted 1,4-Oxathiins
General Method for Oxathiin-S,S-Dioxides
3.3. Oxathiins Ring Opening Experiments
3.3.1. Example Procedure for Base Catalyzed Ring Openings of Oxathiin 5a
3.3.2. Example Procedure for Isomerization of 12Z to 12E
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Acknowledgments
Conflicts of Interest
Sample Availability
References
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# | Scale a | Yield b,c | ||
---|---|---|---|---|
1 | Ar1 = C6H5, 5a | 1 | 74% | |
2 | C6H5, 5a | 4 | 86% d | |
3 | C6H5, 5a | 4 | 75% e | |
4 | 2-I-C6H4, 5b | 2 | 78% | |
5 | 3-Cl-C6H4, 5c | 3 | 76% e | |
6 | 4-NO2-C6H4, 5d | 3 | 62% e | |
7 | 4-CH3-C6H4, 5e | 1 | 76% | |
8 | 4-CH3O-C6H4, 5f | 1 | 44% | |
9 | 4-Br-C6H4, 5g | 1 | 73% | |
10 | 3-CN-C6H4, 5h | 3 | 64% | |
11 | Ar2 = 4-CN-C6H4, 5i | 1 | 69% | |
12 | 4-Br-C6H4, 5j | 1 | 34% | |
13 | 4-F-C6H4, 5k | 1 | 78% | |
14 | 4-NO2-C6H4, 5l | 1 | 62% | |
15 | 2-CF3-C6H4, 5m | 2 | 35% | |
16 | 4-CH3O-C6H4, 5n | 2 | 74% | |
17 | 2-furyl, 5o | 2 | 37% | |
18 | X = 4-Me; Y = 4-NO2; R = Ph, 5p | 1 | 55% | |
19 | X = 2-I; Y = 4-NO2; R = Ph, 5q | 1 | 64% d,e | |
20 | X = 2-I; Y-Ar = 2-thienyl; R = Ph, 5r | 4 | 35% d,e | |
21 | X = 2-I; Y = H; R = tBu, 5s | 3 | 39% d | |
22 | X = 2-I; Y = H; R = Me, 5t | 3 | 38% |
Relative Ratio of Isomers b | ||
---|---|---|
Duration (h) | % 7Z | % 7E |
0 c | 76 | 24 |
24 | 26 | 74 |
48 | 3 | 97 |
72 | 0 | 100 |
C5-C6 (Å) | C5-S (Å) | S-O1 (Å) | S-O2 (Å) | S-C3 (Å) | C3-C2 (Å) | C2-Ob (Å) | O1-Li a (Å) | O2-Li a (Å) | Ob-Li a (Å) | Ob-C6 (Å) | PhC3-C2Ph Dihedral | HC3-C2H Dihedral | |
---|---|---|---|---|---|---|---|---|---|---|---|---|---|
9cis | 1.206 | 1.717 | 1.457 | 1.473 | 1.819 | 1.577 | 1.353 | - | 1.971 | 1.783 | 3.969 | 55.0 | 39.2 |
9cis‡ | 1.250 | 1.715 | 1.460 | 1.484 | 1.839 | 1.574 | 1.379 | - | 1.977 | 1.848 | 2.152 | 38.7 | 23.7 |
10cis | 1.344 | 1.732 | 1.465 | 1.502 | 1.845 | 1.570 | 1.434 | - | 1.915 | 2.152 | 1.426 | 10.7 | 4.7 |
9trans | 1.206 | 1.718 | 1.473 | 1.456 | 1.822 | 1.577 | 1.351 | 1.979 | - | 1.774 | 3.819 | −60.8 | 176.5 |
9trans‡ | 1.250 | 1.716 | 1.486 | 1.459 | 1.831 | 1.574 | 1.376 | 1.974 | - | 1.852 | 2.158 | −76.0 | 161.7 |
10trans | 1.344 | 1.731 | 1.505 | 1.464 | 1.856 | 1.548 | 1.434 | 1.900 | - | 2.287 | 1.423 | −83.3 | 161.1 |
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Nicol, E.A.; Sing, M.; Luu, L.U.; Remigio, E.J.; Mills, M.B.; Schwan, A.L. The Synthesis and Base-Induced Breakdown of Triaryl 1,4-Oxathiins—An Experimental and DFT Study. Molecules 2023, 28, 6180. https://doi.org/10.3390/molecules28176180
Nicol EA, Sing M, Luu LU, Remigio EJ, Mills MB, Schwan AL. The Synthesis and Base-Induced Breakdown of Triaryl 1,4-Oxathiins—An Experimental and DFT Study. Molecules. 2023; 28(17):6180. https://doi.org/10.3390/molecules28176180
Chicago/Turabian StyleNicol, Eric A., Matthew Sing, Lilly U. Luu, Erwin J. Remigio, Michelle B. Mills, and Adrian L. Schwan. 2023. "The Synthesis and Base-Induced Breakdown of Triaryl 1,4-Oxathiins—An Experimental and DFT Study" Molecules 28, no. 17: 6180. https://doi.org/10.3390/molecules28176180