Spin-imposed stereoselection in the photocycloaddition of (Z)- and (E)-cyclooctene to aliphatic aldehydes

Abstract

The simple diastereoselectivity of the photocycloaddition of aliphatic aldehydes to (Z)- and (E)-cyclooctene was analyzed as a function of the substrate concentrations and applied to spin mapping.

Selectivity Control in Electron Spin Inversion Processes: Regio- and Stereochemistry of Paternò−Büchi Photocyclo- additions as a Powerful Tool for Mapping Intersystem Crossing Processes

“…Due to larger endo/exo selectivity from the triplet channel (dr = 5.6) with decreasing temperature, the total endo/exo ratio increases steadily. Similar effects have been reported with cis - and trans -cyclooctene as substrates and aromatic (pure triplet systems), as well as aliphatic, aldehydes …”

“…Similar effects have been reported with cis-and trans-cyclooctene as substrates and aromatic (pure triplet systems), 31 as well as aliphatic, aldehydes. 32…”

Selectivity Control in Electron Spin Inversion Processes: Regio- and Stereochemistry of Paternò−Büchi Photocyclo- additions as a Powerful Tool for Mapping Intersystem Crossing Processes

“…Due to larger endo/exo selectivity from the triplet channel (dr = 5.6) with decreasing temperature, the total endo/exo ratio increases steadily. Similar effects have been reported with cis - and trans -cyclooctene as substrates and aromatic (pure triplet systems), as well as aliphatic, aldehydes …”

“…Similar effects have been reported with cis-and trans-cyclooctene as substrates and aromatic (pure triplet systems), 31 as well as aliphatic, aldehydes. 32…”

Spin‐dependent diastereoselectivity in the photocycloaddition of aldehydes to 2,2‐dimethyl‐2,3‐dihydrofuran

“…In a series of publications, we have recently described the effect of substrate concentration on the spin-selectivity [2] of the Paternò-Büchi reactions of aliphatic aldehydes with 2,3-dihydrofuran [3], allylic alcohols [4], and cyclooctene [5], as well as temperature and viscosity dependence of these reactions [6]. More recently, we have also investigated the 2 H magnetic isotope effect on the stereoselectivity in singlet and triplet photocycloaddition reactions [7].…”

Selectivity Control in Electron Spin Inversion Processes: Regio- and Stereochemistry of Paternò−Büchi Photocyclo- additions as a Powerful Tool for Mapping Intersystem Crossing Processes

“…Due to larger endo/exo selectivity from the triplet channel (dr = 5.6) with decreasing temperature, the total endo/exo ratio increases steadily. Similar effects have been reported with cis - and trans -cyclooctene as substrates and aromatic (pure triplet systems), as well as aliphatic, aldehydes …”

“…Similar effects have been reported with cis-and trans-cyclooctene as substrates and aromatic (pure triplet systems), 31 as well as aliphatic, aldehydes. 32…”

Spin‐dependent diastereoselectivity in the photocycloaddition of aldehydes to 2,2‐dimethyl‐2,3‐dihydrofuran

“…In a series of publications, we have recently described the effect of substrate concentration on the spin-selectivity [2] of the Paternò-Büchi reactions of aliphatic aldehydes with 2,3-dihydrofuran [3], allylic alcohols [4], and cyclooctene [5], as well as temperature and viscosity dependence of these reactions [6]. More recently, we have also investigated the 2 H magnetic isotope effect on the stereoselectivity in singlet and triplet photocycloaddition reactions [7].…”

Selectivity Control in Electron Spin Inversion Processes: Regio- and Stereochemistry of Paternò−Büchi Photocyclo- additions as a Powerful Tool for Mapping Intersystem Crossing Processes

“…Due to larger endo/exo selectivity from the triplet channel (dr = 5.6) with decreasing temperature, the total endo/exo ratio increases steadily. Similar effects have been reported with cis - and trans -cyclooctene as substrates and aromatic (pure triplet systems), as well as aliphatic, aldehydes …”

“…Similar effects have been reported with cis-and trans-cyclooctene as substrates and aromatic (pure triplet systems), 31 as well as aliphatic, aldehydes. 32…”

Spin‐dependent diastereoselectivity in the photocycloaddition of aldehydes to 2,2‐dimethyl‐2,3‐dihydrofuran

“…In a series of publications, we have recently described the effect of substrate concentration on the spin-selectivity [2] of the Paternò-Büchi reactions of aliphatic aldehydes with 2,3-dihydrofuran [3], allylic alcohols [4], and cyclooctene [5], as well as temperature and viscosity dependence of these reactions [6]. More recently, we have also investigated the 2 H magnetic isotope effect on the stereoselectivity in singlet and triplet photocycloaddition reactions [7].…”