Modification of photochemistry by cyclodextrin complexation. Competitive Norrish type I and type II reactions of benzoin alkyl ethers

1986 ◽  
Vol 51 (16) ◽  
pp. 3085-3093 ◽  
Author(s):  
G. Dasaratha Reddy ◽  
G. Usha ◽  
K. V. Ramanathan ◽  
V. Ramamurthy
Keyword(s):  
Type I ◽  
Type Ii ◽  
Cyclodextrin Complexation ◽  
Norrish Type ◽  
Alkyl Ethers

scholarly journals Competition Between Cyclization and Unusual Norrish Type I and Type II Nitro-Acyl Migration Pathways in the Photouncaging of 1-Acyl-7-nitroindoline Revealed by Computations

2020 ◽  
Author(s):  
Pierpaolo Morgante ◽  
Charitha Guruge ◽  
Yannick P. Ouedraogo ◽  
Nasri Nesnas ◽  
Roberto Peverati
Keyword(s):  
Density Functional ◽  
Acyl Migration ◽  
Density Functional Theory Calculations ◽  
Computational Procedure ◽  
Quantum Yields ◽  
Type I ◽  
Type Ii ◽  
Relative Quantum ◽  
Norrish Type ◽  
Migration Pathways

The 7-nitroindolinyl family of caging chromophores has received much attention in the past two decades. However, its uncaging mechanism is still not clearly understood. In this study, we performed state-of-the-art density functional theory calculations to unravel the photo-uncaging mechanism in its entirety, and we compared the probabilities of all plausible pathways. We found competition between a classical cyclization and acyl migration pathways, and here we explain the electronic and steric reasons behind such competition. The migration mechanism possesses the characteristics of a combined Norrish Type I and a 1,6-nitro-acyl variation of a Norrish Type II mechanism, which is reported here for the first time. We also introduced a computational procedure that allows the estimation of intersystem crossing rate constants useful to compare the relative quantum yield of substituted cages. This procedure may pave the way for improved cage designs that possess higher quantum yields and a more efficient agonist release.<br>

Photolysis of 4-Methyl 3-Hexanone and 2-Methoxy 3-Pentanone in Hydrocarbon Solution

1971 ◽  
Vol 49 (8) ◽  
pp. 1310-1314 ◽  
Author(s):  
L. P-Y. Lee ◽  
B. McAneney ◽  
J. E. Guillet
Keyword(s):  
Quantum Yield ◽  
Hydrogen Abstraction ◽  
Type I ◽  
Type Ii ◽  
Cage Effect ◽  
Predominant Type ◽  
Norrish Type ◽  
Hydrocarbon Solution ◽  
Membered Transition State ◽  
Made In

Studies of the photolysis of 4-methyl 3-hexanone and the iso-electronic 2-methoxy 3-pentanone have been made in hydrocarbon solution using light of wavelength 313 nm. The latter compound gives only Norrish type II products with a quantum yield of 0.19 ±.01. The former gives a predominance of type I products with a total quantum yield of 0.23 ±.01 and the quantum yield for type II is reduced to 0.10 ±.01. The predominant type I reaction appears to involve α-scission to give an ethyl and a 2-methyl butyryl radical, which suggests a "cage effect". It is suggested that the reason for the suppression of the type I reaction in 2-methoxy 3-pentanone is the greater ease of γ-hydrogen abstraction due to the presence of the oxygen atom in a six-membered transition state.

Photochemistry of macrocyclic ketones within zeolites: competition between norrish type I and type II reactivity

1991 ◽  
Vol 32 (52) ◽  
pp. 7675-7678 ◽  
Author(s):  
V. Ramamurthy ◽  
Xue-Gong Lei ◽  
Nicholas J. Turro ◽  
Thillairaj J. Lewis ◽  
John R. Scheffer
Keyword(s):  
Type I ◽  
Type Ii ◽  
Norrish Type

Modification of photochemical reactivity through the use of clathrates: the Norrish type I and type II reactions in Dianin's compound

1985 ◽  
Vol 63 (10) ◽  
pp. 2719-2725 ◽  
Author(s):  
P. C. Goswami ◽  
Paul de Mayo ◽  
N. Ramnath ◽  
G. Bernard ◽  
N. Omkaram ◽  
...  
Keyword(s):  
Inclusion Complexes ◽  
Hydrogen Abstraction ◽  
Photochemical Reactions ◽  
Type I ◽  
Type Ii ◽  
Guest Molecules ◽  
Photochemical Reactivity ◽  
Norrish Type ◽  
Restricted Environment ◽  
Dianin's Compound

Dianin's compound (4-p-hydroxyphenyl-2,2,4-trimethylchroman) serves as host in a series of well-defined clathrate inclusion complexes with eleven linear, as well as branched chain, phenyl alkyl ketone guest molecules, chosen for their ability to undergo the Norrish type I and type II photochemical reactions in solution. The photochemical reactivity of the guest ketones within the clathrate cavity was determined by irradiation of the inclusion complexes in the solid state. The results were compared to the photoreactivity of the ketones in polar as well as nonpolar liquid media. In general, the inclusion complex medium brings about an enhancement of type I over type II reactivity and causes an increase in type II fragmentation compared to type II cyclization. This change in reactivity is interpreted as resulting from the relatively restricted environment of the clathrate cavity coupled with the greater motion required for the type II process (γ-hydrogen abstraction) compared to the type I reaction (α-cleavage), as well as from the greater steric requirements for type II cyclization (cyclobutanol formation) as compared to type II cleavage (1,4-hydroxybiradical scission).

scholarly journals Competition Between Cyclization and Unusual Norrish Type I and Type II Nitro-Acyl Migration Pathways in the Photouncaging of 1-Acyl-7-nitroindoline Revealed by Computations

2020 ◽  
Author(s):  
Pierpaolo Morgante ◽  
Charitha Guruge ◽  
Yannick P. Ouedraogo ◽  
Nasri Nesnas ◽  
Roberto Peverati
Keyword(s):  
Density Functional ◽  
Acyl Migration ◽  
Density Functional Theory Calculations ◽  
Computational Procedure ◽  
Quantum Yields ◽  
Type I ◽  
Type Ii ◽  
Relative Quantum ◽  
Norrish Type ◽  
Migration Pathways

The 7-nitroindolinyl family of caging chromophores has received much attention in the past two decades. However, its uncaging mechanism is still not clearly understood. In this study, we performed state-of-the-art density functional theory calculations to unravel the photo-uncaging mechanism in its entirety, and we compared the probabilities of all plausible pathways. We found competition between a classical cyclization and acyl migration pathways, and here we explain the electronic and steric reasons behind such competition. The migration mechanism possesses the characteristics of a combined Norrish Type I and a 1,6-nitro-acyl variation of a Norrish Type II mechanism, which is reported here for the first time. We also introduced a computational procedure that allows the estimation of intersystem crossing rate constants useful to compare the relative quantum yield of substituted cages. This procedure may pave the way for improved cage designs that possess higher quantum yields and a more efficient agonist release.<br>

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