Low energy conformations of two carbohydrate-based oxepines were characterized by computational methods and 3JH,H coupling constant analysis. Oxepine reactivity in Ferrier reactions was correlated with percentage vinylogous anomeric effect (VAE).
Ferrier reactions follow a mechanistic pathway whereby
Lewis acid
activation of a cyclic enol ether facilitates departure of an allylic
leaving group to form a glycosyl Ferrier cation. Attack on the Ferrier
cation provides a new acetal linkage concurrent with the transposition
of the alkene moiety. The idiosyncratic outcomes of Ferrier reactions
of seven-membered ring carbohydrate-based oxepines prompted an investigation
of its corresponding septanosyl Ferrier cation. Experiments that characterized
the ion, including gas-phase cryogenic IR spectroscopy matched with
density functional theory-calculated spectra of candidate cation structures,
as well as product analysis from solution-phase Ferrier reactions,
are reported here. Results from both approaches revealed an inclination
of the seven-membered ring cation to contract to five-membered ring
structures. Gas-phase IR spectra matched best to calculated spectra
of structures in which five-membered dioxolenium formation opened
the oxepine ring. In the solution phase, an attack on the ion by water
led to an acyclic enal that cyclized to a C-methylene-aldehydo
arabinofuranoside species. Attack by allyl trimethylsilane, on the
other hand, was diastereoselective and yielded a C-allyl septanoside.
The synthesis and crystal structures of three new disubstituted [13]-macrodilactones, namely, trans-4,8-dimethyl-1,10-dioxacyclotridec-5-ene-2,9-dione, C13H20O4, I, cis-4-(4-bromophenyl)-13-methyl-1,10-dioxacyclotridec-5-ene-2,9-dione C18H21BrO4, II, and trans-11-methyl-4-phenyl-1,10-dioxacyclotridec-5-ene-2,9-dione, C18H22O4, III, are reported and their conformations are put in the context of other [13]-macrodilactone structures reported previously. Together, they show that the number, location, and relative disposition of groups attached at the termini of planar units of the [13]-macrodilactones subtly influence their aspect ratios.
A Ni-catalyzed
cross-coupling is utilized as a reversed strategy
for the homogeneous deprotection of benzyl ethers. The reaction is
accelerated in batch using microwave heating or in flow using superheating
in a plug flow reactor to achieve the desired (hetero)aromatic alcohols
bearing heterocycles, alkenes, and ethers within 1 h. This work highlights
an alternative debenzylation strategy in flow for cases where hydrogenation
using heterogeneous catalysts is not a viable option.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.