Scalable total synthesis of piceatannol-3'-O-β-D-glucopyranoside and the 4'-methoxy congener thereof: An early stage glycosylation strategy

Synthesis ◽  
2021 ◽  
Author(s):  
Jianfeng Li ◽  
Xiaoting Wang ◽  
Rongping Zhang ◽  
Lei Chen
Keyword(s):  
Total Synthesis ◽  
Heck Reaction ◽  
Early Stage ◽  
Phenolic Glycoside ◽  
Acidic Conditions ◽  
Scalable Synthesis ◽  
Glycosylation Reaction

Scalable synthesis of piceatannol-3'-O-β-D-glucopyranoside and the 4'-methoxy congener thereof were achieved. This route features an early implemented Fischer-like glycosylation reaction, a regioselective iodination of phenolic glycoside under strongly acidic conditions, a highly telescoped route to access the styrene derivative and a key Mizoroki-Heck reaction to render the desired coupled products in high overall yield.

Scalable Synthesis of Amaryllidaceae Isocarbostyril Alkaloids from Enantiomerically Pure 7-Azabicyclo[2.2.1]heptanone Scaffold: Total Synthesis of (+)-7-Deoxypancratistatin

Synlett ◽  
2018 ◽  
Vol 29 (06) ◽  
pp. 805-809 ◽  
Author(s):  
Ganesh Pandey ◽  
Rushil Fernandes ◽  
Debasis Dey
Keyword(s):  
Total Synthesis ◽  
Early Stage ◽  
Hydroxyl Groups ◽  
Attractive Feature ◽  
Enantiomerically Pure ◽  
Structural Framework ◽  
Ring Junction ◽  
Scalable Synthesis ◽  
Optically Pure

A conceptually new and scalable strategy (ten linear steps, 13.9% overall yield) has been developed to synthesize (+)-7-deoxy­pancratistatin from optically pure 7-azabicyclo[2.2.1]heptanone scaffold. The crucial trans-B–C ring junction was fixed at an early stage of the synthesis by exploiting the rigid bicyclic structural framework of the starting precursor. Stereoselective installation of hydroxyl groups around the perimeter of the cyclohexenyl C-ring involved sequential epoxidation–phenylselenylation–oxydeselenylation sequence followed by dihydroxylation. The most attractive feature of this synthesis is the use of a protection–deprotection step only at the penultimate step making the protocol very efficient and atom economical.

First total synthesis of antihypertensive natural products S-(+)-XJP and R-(−)-XJP

2014 ◽  
Vol 12 (37) ◽  
pp. 7338-7344 ◽  
Author(s):  
Chaolei Wang ◽  
Guoxiang Wei ◽  
Xue Yang ◽  
Hequan Yao ◽  
Jieyun Jiang ◽  
...  
Keyword(s):  
Natural Products ◽  
Total Synthesis ◽  
Heck Reaction ◽  
Intramolecular Heck Reaction

The first total synthesis of S-(+)-XJP and R-(−)-XJP has been achieved via intramolecular Heck reaction. A latent functionality strategy was implemented to circumvent the racemization in this endeavor.

scholarly journals Diastereoselective Total Synthesis of (+)-Raputindole A: An Iridium- Catalyzed Cyclization Approach

2020 ◽  
Author(s):  
Ronaldo Pilli ◽  
Juliana Lira Luna Freire Regueira ◽  
Luiz Fernando Silva Jr.
Keyword(s):  
Total Synthesis ◽  
Heck Reaction ◽  
Enzymatic Resolution ◽  
Enantiomerically Pure ◽  
Tricyclic Core ◽  
Benzylic Alcohol ◽  
Convergent Approach

This work describes the total synthesis of Raputindole A <b>(1)</b> through a convergent approach which features: 1) an iridium-catalyzed cyclization to assembly the tricyclic core of the northern part, 2) enzymatic resolution to secure the preparation of enantiomerically pure benzylic alcohol, 3) installation of the butenyl substituent via methallylation of the corresponding benzylic carbocation and coupling of the northern and southern parts via Heck reaction. (+)-Raputindole A <b>(1)</b> was prepared in 10 steps (LLS) and 10% overall yield.

Bioinspired Total Synthesis of Marine Anti-Cancer Meroterpenoids Dysideanone B and Dysiherbol A and Structure Revision of Dysiherbol A

Synlett ◽  
2021 ◽  
Author(s):  
Zhaoyong Lu ◽  
Chuanke Chong
Keyword(s):  
Total Synthesis ◽  
Heck Reaction ◽  
Recent Progress ◽  
Benzyl Bromide ◽  
Radical Cyclization ◽  
Ethoxy Group ◽  
Anti Cancer ◽  
Structure Revision ◽  
A Site ◽  
Intramolecular Heck Reaction

Our recent progress on the total synthesis of marine anti-cancer sesquiterpene quinone/hydroquinone dysideanone B and dysiherbol A was briefly highlighted. This success relied on some key transformations. The union of the terpene and quinone/hydroquinone moieties was realized through a site and stereoselective α-position alkylation of Wieland–Miescher ketone derivative with a bulky benzyl bromide. The 6/6/6/6-tetracycle of dysideanone B was constructed using an intramolecular radical cyclization and the 6/6/5/6-fused core structure of dysiherbol A was forged by an intramolecular Heck reaction, respectively. The possible origin of ethoxy group in dysideanone B was revealed by mimicking the isolation conditions at a late-stage. The structure of dysiherbol A was revised through the total synthesis of this natural product. Schmalz’s synthesis of dysiherbol A was also included.

scholarly journals Total Synthesis of Caprazamycin A: Practical and Scalable Synthesis of syn-β-Hydroxyamino Acids and Introduction of a Fatty Acid Side Chain to 1,4-Diazepanone

2019 ◽  
Vol 141 (21) ◽  
pp. 8527-8540 ◽  
Author(s):  
Hugh Nakamura ◽  
Chihiro Tsukano ◽  
Takuma Yoshida ◽  
Motohiro Yasui ◽  
Shinsuke Yokouchi ◽  
...  
Keyword(s):  
Fatty Acid ◽  
Total Synthesis ◽  
Side Chain ◽  
Hydroxyamino Acids ◽  
Scalable Synthesis

scholarly journals Radiosynthesis of [18F]-Labelled Pro-Nucleotides (ProTides)

Molecules ◽  
2020 ◽  
Vol 25 (3) ◽  
pp. 704
Author(s):  
Alessandra Cavaliere ◽  
Katrin C. Probst ◽  
Stephen J. Paisey ◽  
Christopher Marshall ◽  
Abdul K. H. Dheere ◽  
...  
Keyword(s):  
Total Synthesis ◽  
Pet Imaging ◽  
Early Stage ◽  
Proof Of Concept ◽  
Synthesis Time ◽  
Positron Emission ◽  
Anti Cancer ◽  
Radiochemical Yields ◽  
Radiochemical Synthesis

Phosphoramidate pro-nucleotides (ProTides) have revolutionized the field of anti-viral and anti-cancer nucleoside therapy, overcoming the major limitations of nucleoside therapies and achieving clinical and commercial success. Despite the translation of ProTide technology into the clinic, there remain unresolved in vivo pharmacokinetic and pharmacodynamic questions. Positron Emission Tomography (PET) imaging using [18F]-labelled model ProTides could directly address key mechanistic questions and predict response to ProTide therapy. Here we report the first radiochemical synthesis of [18F]ProTides as novel probes for PET imaging. As a proof of concept, two chemically distinct radiolabelled ProTides have been synthesized as models of 3′- and 2′-fluorinated ProTides following different radiosynthetic approaches. The 3′-[18F]FLT ProTide was obtained via a late stage [18F]fluorination in radiochemical yields (RCY) of 15–30% (n = 5, decay-corrected from end of bombardment (EoB)), with high radiochemical purities (97%) and molar activities of 56 GBq/μmol (total synthesis time of 130 min.). The 2′-[18F]FIAU ProTide was obtained via an early stage [18F]fluorination approach with an RCY of 1–5% (n = 7, decay-corrected from EoB), with high radiochemical purities (98%) and molar activities of 53 GBq/μmol (total synthesis time of 240 min).

scholarly journals Efficient Route to 4a-Methyltetrahydrofluorenes: A Total Synthesis of (.+-.)-Dichroanal B via Intramolecular Heck Reaction.

ChemInform ◽  
2006 ◽  
Vol 37 (34) ◽  
Author(s):  
Loic Planas ◽  
Muneto Mogi ◽  
Hirofumi Takita ◽  
Tetsuya Kajimoto ◽  
Manabu Node
Keyword(s):  
Total Synthesis ◽  
Heck Reaction ◽  
Efficient Route ◽  
Intramolecular Heck Reaction

Total synthesis of (±)-9-deoxygoniopypyrone. Application of the iodocyclofunctionalization reaction of bold α-allenic alcohol derivatives

1998 ◽  
Vol 76 (1) ◽  
pp. 94-101 ◽  
Author(s):  
Richard W Friesen ◽  
Suzanne Bissada
Keyword(s):  
Total Synthesis ◽  
Primary Alcohol ◽  
Silyl Ether ◽  
Protecting Group ◽  
Acetylenic Ester ◽  
The Third ◽  
Vicinal Diol ◽  
Epoxide Opening ◽  
Vinyl Iodide ◽  
Acidic Conditions

The synthesis of ( ±)-9-deoxygoniopypyrone (1) from the α-allenic alcohol 5 is described. Iodocyclofunctionaliztion of the N-tosyl carbamate derivative of 5 using I2 and Ag2CO3 provided, in a highly diastereoselective and regioselective fashion, the vinyl iodo syn-vicinal diol 4. Two routes were explored in order to introduce the third stereogenic centre in the molecule. Reductive deiodination of the vinyl iodide and diastereoselective epoxidation of the derived acetonide14 using mCPBA provided a mixture of epoxides 15 and 16 (2:1) in which the desired threo diastereomer predominated. Alternatively, dihydroxylation of acetonide 14 (OsO4, NMO) yielded a mixture of diols 21 and 22 (2:3) which were separated after monosilylation (TBDMSCl) of the primary alcohol. The major silyl ether erythro diastereomer 24 was converted to the desired epoxide 15 by mesylation (MsCl, Et3N) and epoxide formation (TBAF) with inversion of stereochemistry. The minor threo diastereomer 23 was also converted to the desired epoxide 15 (TBAF; ArSO2Cl; NaOMe). Epoxide opening was effected with lithium acetylide and the resulting alkyne 27 was carbonylated (MeLi, ClCO2Me) to afford the α , β-acetylenic ester 28. Semi hydrogenation over Lindlar's catalyst followed by protecting- group removal under acidic conditions provided ( ±)-8-epigoniodiol 30. Finally, conversion of 30 to ( ±)-9-deoxygoniopypyrone 1 was effected under basic conditions (DBU).Key words: ( ±)-9-deoxygoniopypyrone, α-allenic alcohol, iodocyclofunctionalization, syn-diol.

Sign in / Sign up

Export Citation Format

Share Document