Photochemistry of 2-Nitrobenzyl Enol Ethers:  Oxidative CC Bond Scission

Abstract

[reaction: see text] 2-Nitrobenzyl enol ethers, when photolyzed in the presence of air, result in an oxidative C=C bond scission, forming a ketone as the major product (>60% yield). Enol release leads to the aldehyde as the minor product.

A Cytidine Phosphoramidite with Protected Nitroxide Spin Label: Synthesis of a Full‐Length TAR RNA and Investigation by In‐Line Probing and EPR Spectroscopy

“…[57,58] In this process, radicals obtained from 9 recombine with the nitroxidet o form the O-alkylated product 11.C ompound 9 is accessible from 2-nitrobenzyl alcohol by Pummerer rearrangement (8) and chlorination (Scheme1). [59,60] Subsequently,c ompound 11 was challenged by reagents typical for oligonucleotide synthesis and ligation: ammonia, iodine, triethylamine trihydrofluoride, dithiothreitol, and trifluoroacetic acid. Compound 11 provedt ob es ufficiently stable (see Supporting Information S6).…”

Photo-Responsive Micelles with Controllable and Co-Release of Carbon Monoxide, Formaldehyde and Doxorubicin

“…In total, 10% (v/v) fetal bovine serum (ExCell Bio, Suzhou, China) and 1% (v/v) penicillin/Streptomycin Solution purchased from Beyotime biotechnology (Shanghai, China) were added to cell culture medium (DMEM) (Beyotime biotechnology, Shanghai, China). Compound A [31], 1-(chloromethoxymethyl)-4,5-dimethoxy-2-nitrobenzene [32,33] and polyethylene oxide macromolecular chain transfer reagent [34] were synthesized according to the methods reported in the literature.…”

“…The above mass spectrometry results are consistent with the reported photo-degradation process of 3-HF derivatives as CO donor molecules. [32] Figure 4a shows that only the ionic peak of compound B is found by mass spectrometry analysis without light. These outcomes not only prove the good stability of the donor molecules under dark conditions, but also can photo-responsively co-deliver CO and FA.…”

Catalytic Asymmetric Dihydroxylation of Enamides and Application to the Total Synthesis of (+)‐Tanikolide

“…[3] Enamides 6 a-6 c containing a phenyl substituent at the R 1 position were effective substrates, with a 2thienyl group at R 2 (entry 3) providing a higher enantioselectivity than a methyl (entry 1) or an ethyl group (entry 2). Enamides 6 d-6 i containing aliphatic groups (simple alkyl, oxygenated alkyl) at R 1 and (hetero)aryl groups (phenyl, ptolyl, 3-carboethoxyphenyl, 2-thienyl) at R 2 proved to be especially competent substrates, providing products in generally good yields with uniformly high enantioselectivities (entries [4][5][6][7][8][9]. Comparison of the present method with asymmetric dihydroxylation of 1,1-disubstituted alkenes is informative.…”

“…To ensure high enantioselectivity in the dihydroxylation event, the substrate 3 must be obtained in high stereoisomeric purity. [6] Unfortunately, existing methods to prepare these compounds typically proceed with poor E/Z stereoselectivity, [7][8][9] and the resulting geometric isomers can be difficult to separate. Partial solutions to these problems have been described recently.…”