NDLI: A Time-Resolved Spectroscopic Study of the Bichromophoric Phototrigger 3′,5′-Dimethoxybenzoin Diethyl Phosphate: Interaction Between the Two Chromophores Determines the Reaction Pathway

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A Time-Resolved Spectroscopic Study of the Bichromophoric Phototrigger 3′,5′-Dimethoxybenzoin Diethyl Phosphate: Interaction Between the Two Chromophores Determines the Reaction Pathway

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A Time-Resolved Spectroscopic Study of the Bichromophoric Phototrigger 3′,5′-Dimethoxybenzoin Diethyl Phosphate: Interaction Between the Two Chromophores Determines the Reaction Pathway

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Kwok, Wai Ming An, Hui-ying Fu, Michael Yunyi Toy, Patrick H. Guan, Xiangguo Ma, Chensheng Phillips, David Lee
Description	Author Affiliation: Ma C ( Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, P. R. China.)
Abstract	3′,5′-Dimethoxybenzoin (DMB) is a bichromophoric system that has widespread application as a highly efficient photoremovable protecting group (PRPG) for the release of diverse functional groups. The photodeprotection of DMB phototriggers is remarkably clean, and is accompanied by the formation of a biologically benign cyclization product, 3′,5′-dimethoxybenzofuran (DMBF). The underlying mechanism of the DMB deprotection and cyclization has, however, until now remained unclear. Femtosecond transient absorption (fs-TA) spectroscopy and nanosecond time-resolved resonance Raman $(ns-TR^{3})$ spectroscopy were employed to detect the transient species directly, and examine the dynamic transformations involved in the primary photoreactions for DMB diethyl phosphate (DMBDP) in acetonitrile $(CH_{3}CN).$ To assess the electronic character and the role played by the individual sub-chromophore, that is, the benzoyl, and the di-meta-methoxybenzylic moieties, for the DMBDP deprotection, comparative fs-TA measurements were also carried out for the reference compounds diethyl phosphate acetophenone (DPAP), and 3′,5′-dimethoxybenzylic diethyl phosphate (DMBnDP) in the same solvent. Comparison of the fs-TA spectra reveals that the photoexcited DMBDP exhibits distinctly different spectral character and dynamic evolution from those of the reference compounds. This fact, combined with the related steady-state spectral and density functional theoretical results, strongly suggests the presence in DMBDP of a significant interaction between the two sub-chromophores, and that this interaction plays a governing role in determining the nature of the photoexcitation and the reaction channel of the subsequent photophysical and photochemical transformations. The $ns-TR^{3}$ results and their correlation with the fs-TA spectra and dynamics provide evidence for a novel concerted deprotection–cyclization mechanism for DMBDP in $CH_{3}CN.$ By monitoring the direct generation of the transient DMBF product, the cyclization time constant was determined unequivocally to be ≈1 ns. This indicates that there is little relevance for the long-lived intermediates (>10 ns) in giving the DMBF product, and excludes the stepwise mechanism proposed in the literature as the major pathway for the DMB cyclization reaction. This work provides important new insights into the origin of the 3′,5′-dimethoxy substitution effect for the DMB photodeprotection. It also helps to clarify the many different views presented in previous mechanistic studies of the DMB PRPGs. In addition to this, our fs-TA results on the reference compound DMBnDP in $CH_{3}CN$ provide the first direct observation (to the best of our knowledge) showing the predominance of a prompt (≈2 ps) heterolytic bond cleavage after photoexcitation of meta-methoxybenzylic compounds. This provides insight into the long-term controversies about the photoinitiated dissociation mode of related substituted benzylic compounds.
ISSN	09476539
e-ISSN	15213765
Journal	Chemistry - A European Journal
Issue Number	17
Volume Number	16
Language	English
Publisher	Wiley-VCH;ChemPubSoc Europe
Publisher Date	2010-05-03
Publisher Place	Germany
Access Restriction	Open
Subject Keyword	Benzene Derivatives Chemistry Chemical Synthesis Models, Chemical Organophosphorus Compounds Spectrum Analysis Photochemical Processes Time Factors Research Support, Non-U.S. Gov't
Content Type	Text
Resource Type	Article
Subject	Organic Chemistry Catalysis

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