Chiral induction in photochemical reactions. 10. The principle of isoinversion: a model of stereoselection developed from the diastereoselectivity of the Paterno-Buechi reaction

Buschmann, Helmut; Scharf, Hans‐Dieter; Hoffmann, Norbert; Plath, Martin; Runsink, Jan

doi:10.1021/ja00196a048

Cited by 118 publications

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“…Their intersection is close to the x-axis and the corresponding H ≠ and S ≠ values have opposite signs. 51,81,88,89,90,210 The observation of such a relationship in the present case indicates that the photooxygenations of investigated enecarbamates 205,207 possess the same reaction mechanism. In Figure 11, the isoselective relationship is depicted.…”

Section: Methodssupporting

confidence: 57%

Studies in organic and physical photochemistry – an interdisciplinary approach

Oelgemöller

Hoffmann

2016

Org. Biomol. Chem.

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Traditionally, organic photochemistry when applied to synthesis strongly interacts with physical chemistry. The aim of this review is to illustrate this very fruitful interdisciplinary approach and cooperation. A profound understanding of the photochemical reactivity and reaction mechanisms is particularly helpful for optimization and application of these reactions. Some typical reactions and particular aspects are reported such as the Norrish-Type II reaction and the Yang cyclization and related transformations, the [2 + 2] photocycloadditions, particularly the Paternò-Büchi reaction, photochemical electron transfer induced transformations, different kinds of catalytic reactions such as photoredox catalysis for organic synthesis and photooxygenation are discussed. Particular aspects such as the structure and reactivity of aryl cations, photochemical reactions in the crystalline state, chiral memory, different mechanisms of hydrogen transfer in photochemical reactions or fundamental aspects of stereoselectivity are discussed. Photochemical reactions are also investigated in the context of chemical engineering. Particularly, continuous flow reactors are of interest. Novel reactor systems are developed and modeling of photochemical transformations and different reactors play a key role in such studies. This research domain builds a bridge between fundamental studies of organic photochemical reactions and their industrial application.

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Section: Methodssupporting

confidence: 57%

Studies in organic and physical photochemistry – an interdisciplinary approach

Oelgemöller

Hoffmann

2016

Org. Biomol. Chem.

Self Cite

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“…The simulations do not indicate an abrupt change in the selectivity correlation as is the case in isoinversion curves, [1] but an inversion region as described by Hale and Ridd. [7] From our model we expect this inversion region to lie outside the experimental window for many substrate combinations, either in photochemical or thermal reactions.…”

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confidence: 49%

“…[1] The influence of the excited-state spin multiplicity was not observed in these studies as substrates with high intersystem crossing (ISC) rates were used and thus exclusive (bimolecular) triplet reactions were expected. [2] However, the ISC-process from the triplet 1,4-biradical (2-oxatetramethylene), [3] which is necessary to form the closed-shell product, was not discussed as a further possible selection step in the context of the isoinversion principle.…”

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confidence: 99%

“…[5] Despite several attempts to understand these effects theoretically, [1] their origin is still debatable. [6] A simplified model interprets the inversion points in the selectivity/temperature correlation as changes between two selection stages that are controlled to a different by the respective differences in activation enthalpy and entropy degree.…”

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confidence: 99%

“…[6] A simplified model interprets the inversion points in the selectivity/temperature correlation as changes between two selection stages that are controlled to a different by the respective differences in activation enthalpy and entropy degree. [1] Alternatively inversion regions can be postulated which result from a change in the rate-determining step. [7] In recent years we have analyzed closely the mechanism of the terminal bond-forming step in triplet [22] photocycloadditions with an emphasis on the non-induced (™simple∫) diastereoselectivity.…”

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confidence: 99%

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