An official website of the United States government
Photochemical electrocyclization reactions are valued for both their ability to produce structurally complex molecules and their central role in elucidating fundamental mechanistic principles of photochemistry. We present herein a highly enantioselective 6π photoelectrocyclization catalyzed by a chiral Ir(III) photosensitizer. This transformation was successfully realized by engineering a strong hydrogen-bonding interaction between a pyrazole moiety on the catalyst and a basic imidazolyl ketone on the substrate. To shed light on the origin of stereoinduction, we conducted a comprehensive investigation combining experimental and computational mechanistic studies. Results from density functional theory calculations underscore the crucial role played by the prochirality and the torquoselectivity in the electrocyclization process as well as the steric demand in the subsequent [1,4]-H shift step. Our findings not only offer valuable guidance for developing chiral photocatalysts but also serve as a significant reference for achieving high levels of enantioselectivity in the 6π photoelectrocyclization reaction.
more »
« less
Metallocarbenes as Substituents in 8‐Electron Electrocyclizations
Abstract Density functional theory was used to elucidate the mechanism and the pericyclicity of chromium‐catalyzed bicyclization reactions that purportedly involve 8‐electron electrocyclization steps. Our computational results indicate that these reactions do indeed proceed via 8‐electron electrocyclization rather than an alternative pathway involving 4‐electron electrocyclization followed by Cope rearrangement. The role of C=[M] groups on the electrocyclization, specifically its pericyclicity, was examined in detail using modern theoretical tools.
more »
« less
- Award ID(s):
- 2154083
- PAR ID:
- 10492051
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- European Journal of Organic Chemistry
- Volume:
- 27
- Issue:
- 7
- ISSN:
- 1434-193X
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Abstract The combination of electrocyclizations and cycloadditions accounts for the formation of a range of fascinating natural products. Cascades consisting of 8π electrocyclizations followed by a 6π electrocyclization and a cycloaddition are relatively common. We now report the synthesis of the tetramic acid PF‐1018 through an 8π electrocyclization, the product of which is immediately intercepted by a Diels–Alder cycloaddition. The success of this pericyclic cascade was critically dependent on the substitution pattern of the starting polyene and could be rationalized through DFT calculations. The completion of the synthesis required the instalment of a trisubstituted double bond by radical deoxygenation. An unexpected side product formed through 4‐exo‐trig radical cyclization could be recycled through an unprecedented triflation/fragmentation.more » « less
-
Abstract The reaction of an aryne with an alkyne to generate a benzocyclobutadiene (BCB) intermediate is rare. We report here examples of this reaction, revealed by Diels–Alder trapping of the BCB by either pendant or external electron‐deficient alkynes. Mechanistic delineation of the reaction course is supported by DFT calculations. A three‐component process joining the benzyne first with an electron‐rich and then with an electron‐poor alkyne was uncovered. Reactions in which the BCB functions in a rarely observed role as a 4π diene component in Diels–Alder reactions are reported. The results also shed new light on aspects of the hexadehydro‐Diels–Alder reaction used to generate the benzynes.more » « less
-
Significance Metabolic engineering benefits from the tunable and tightly controlled transformations afforded by biological systems. However, these reactions have generally been limited to naturally occurring pathways and products. In this work, we coopt metabolic electron transfer fromShewanella oneidensisto control the activity of an exogenous metal catalyst in an abiotic reaction scheme: atom-transfer radical polymerization. In the presence ofS. oneidensis, polymerizations exhibited well-defined kinetics and yielded polymers with controlled molecular weights and low polydispersities. Additionally, polymerization activity was dependent on electroactive metabolism and specific electron transport proteins, both of which provide handles to control material synthesis. This work serves as a proof-of-principle toward expanding the scope of reactions available to metabolic engineers to include previously discovered transition-metal–catalyzed reactions.more » « less
-
Abstract We have used measurements of the Defense Meteorological Satellite Program (DMSP) satellites to study variations of electron temperature in the subauroral ionosphere during the magnetic storm on 17–25 March 2015. This magnetic storm had a long recovery phase of 7 days, and the ionospheric behavior over the entire storm time was seldom investigated. In this study, we find that the electron temperature at subauroral latitudes was continuously enhanced for 8 days, from the storm onset to the end of the recovery phase. The maximum electron temperature during the storm times was 1000–4000 K higher than the maximum electron temperature during quiet times. This long‐lasting enhancement of subauroral electron temperature was attributed to energy transfer among the solar wind, magnetosphere, ring current, plasmasphere, and ionosphere driven by high‐speed solar wind streams and fluctuating interplanetary magnetic field during the entire 8‐day period of the storm. The electron temperature enhancements were quite symmetric in the post‐midnight sector but became strongly asymmetric near dawn between the southern and northern hemispheres. The asymmetric enhancements of electron temperature near dawn may be related to the magnetic declination and the daytime midlatitude trough in the southern hemisphere. Large daily variations of maximum electron temperature in the post‐midnight sector were observed and may be related to the offset between geomagnetic and geographic latitudes. These DMSP observations provide new insight on ionospheric response to intense magnetic storms.more » « less
