“…This reaction is largely unprecedented and should also be applicable to other methylene (or alkylidene) oxacycles. An analogous ring-opening of a 2-alkylidene tetrahydrofuran treated with LDA in the absence of trimethylaluminum has been previously observed, but only as a minor pathway. , 1 …”
“…This reaction is largely unprecedented and should also be applicable to other methylene (or alkylidene) oxacycles. An analogous ring-opening of a 2-alkylidene tetrahydrofuran treated with LDA in the absence of trimethylaluminum has been previously observed, but only as a minor pathway. , 1 …”
“…Protection of the 3, 4‐hydroxyl groups of 2‐deoxy‐D‐ribose with 2‐methoxypropene followed by oxidation at the anomeric position with iodine in the presence of potassium carbonate afforded 2‐deoxy‐D‐ribono‐1, 5‐lactone 7 in 76 % overall yield on a multigram scale. As a comparison, the oxidation previously reported [10] by aqueous bromine in the presence of calcium carbonate proceeded in a much lower yield (<50 %). With the completion of the lactone subunit, our attention was then focused on the synthesis of the 5‐formyltetrahydroquinoline framework (A/B rings) 5 as shown in Scheme 3.…”
Section: Resultsmentioning
confidence: 74%
“…The synthetic sequence commenced with the formation of the known lactone 7 from 2‐deoxy‐ D ‐ribose ( 8 ) following a modified procedure from Yadav's report [10] (Scheme 3). Protection of the 3, 4‐hydroxyl groups of 2‐deoxy‐D‐ribose with 2‐methoxypropene followed by oxidation at the anomeric position with iodine in the presence of potassium carbonate afforded 2‐deoxy‐D‐ribono‐1, 5‐lactone 7 in 76 % overall yield on a multigram scale.…”
The concise and efficient synthesis of tetrahydroquinoline alkaloids lycibarbarines A−C has been accomplished in four steps from a common intermediate derived from commercially available 2‐deoxy‐D‐ribose and 8‐hydroxyquinoline. For the synthesis of the unique tetracyclic spiro‐heterocycle skeleton we employed a synthetic strategy that features two key transformations: iodomethyllithium‐based homologation of lactone / N‐alkylation to access tetracyclic spiro‐heterocycle skeleton in one step and one‐pot acetonide deprotection, hemiacetal formation, and spirocyclization cascade process.
“…In this study, GA3P could be utilized by 2-deoxy- d -ribose 5-phosphate aldolase (DERA) through aldol addition with acetaldehyde, generating 2-deoxy- d -ribose 5-phosphate (DR5P) to produce 2-deoxy- d -ribose (DR) by dephosphorylation of DR5P. DR can be used in the treatment of cardiovascular diseases, can play an important role in drug transport and identification between drugs and targets, and can be used for the synthesis of nucleoside antiviral and antitumor drugs, such as Zidovudine, Lamivudine, Stavudine, and Decitabine. , DHAP could be utilized by DHAP-dependent aldolases through aldol additions with aldehydes, generating various rare ketose 1-phosphates (RK1Ps) to produce different rare ketoses (e.g., d -allulose, d -sorbose, d -ribulose, l -tagatose, l -xylulose, and l -fructose). These rare ketoses can be used as food additives as low-calorie sweeteners, cancer cell suppressors, and building blocks for anticancer and antiviral drugs. , …”
Asymmetric C–C bond formation mediated by aldolase
provides
one of the most efficient ways to produce valuable chemicals in biomanufacturing.
Dihydroxyacetone phosphate (DHAP) and d-glyceraldehyde 3-phosphate
(GA3P) are two important platform compounds for asymmetric C–C
bond formation. In this study, several artificial ATP-free in vitro
synthetic enzymatic biosystems were constructed to produce valuable
chemicals via facile synthesis of GA3P and DHAP from starch and pyrophosphate.
Six cascade enzymes were used for the biotransformation of starch
and pyrophosphate to GA3P or DHAP: alpha-glucan phosphorylase (αGP),
phosphoglucomutase (PGM), phosphoglucose isomerase (PGI), pyrophosphate
phosphofructokinase (PPi-PFK), d-fructose 1,6-bisphosphate
aldolase (FruA), and triosephosphate isomerase (TIM). These two compounds
were then used to produce various chemicals, including 2-deoxy-d-ribose (DR) and rare ketoses. After the optimization of reaction
conditions, ∼23.2 mM DR with a product yield of 96.7% and 15.2
mM d-allulose with a product yield of 95.0% were produced,
both achieving near-stoichiometric yields through downstream aldol
additions and dephosphorylation reactions in one pot. In addition,
more than 80% of the product yields of DR and many rare ketoses, such
as d-allulose, l-tagatose, d-sorbose, l-fructose, and d-xylulose, from high concentrations
of substrates were obtained, showing high industrial potential. This
in vitro biomanufacturing platform may provide a promising and cost-effective
approach for biomanufacturing value-added chemicals through asymmetric
C–C bond formation in the near future.
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