Asymmetric Total Synthesis of (+)-Coprophilin

Synthesis ◽  
2017 ◽  
Vol 50 (06) ◽  
pp. 1301-1306 ◽  
Author(s):  
Isamu Shiina ◽  
Yuma Umezaki ◽  
Takatsugu Murata ◽  
Kyohei Suzuki ◽  
Takayuki Tonoi
Keyword(s):  
Total Synthesis ◽  
Aldol Reaction ◽  
Alder Reaction ◽  
Diels Alder ◽  
Core Structure ◽  
Asymmetric Total Synthesis ◽  
Diels Alder Reaction ◽  
Anticoccidial Agent

In this paper, we report the first total synthesis of (+)-coprophilin, an anticoccidial agent, by constructing the chiral linear precursor via a Mukaiyama–Evans aldol reaction and a stereoselective intramolecular Diels–Alder reaction. The proposed method can be used to provide large amounts of (+)-coprophilin, which exhibits a 3,4,5,6,7-pentasubstituted Δ1,2-octalin core structure.

Catalytic Asymmetric Total Synthesis of (+)- and (−)-Paeoveitol via a Hetero-Diels–Alder Reaction

2017 ◽  
Vol 19 (3) ◽  
pp. 429-431 ◽  
Author(s):  
Tian-Ze Li ◽  
Chang-An Geng ◽  
Xiu-Juan Yin ◽  
Tong-Hua Yang ◽  
Xing-Long Chen ◽  
...  
Keyword(s):  
Total Synthesis ◽  
Alder Reaction ◽  
Diels Alder ◽  
Asymmetric Total Synthesis ◽  
Diels Alder Reaction ◽  
Catalytic Asymmetric

An Asymmetric Total Synthesis of D-Homo Steroids Involving a Lewis Acid Directed Diels-Alder Reaction

1978 ◽  
Vol 8 (7) ◽  
pp. 427-436 ◽  
Author(s):  
Noal Cohen ◽  
Bruce L. Banner ◽  
Wayne F. Eichel ◽  
Zdenek Valenta ◽  
Robert A. Dickinson
Keyword(s):  
Total Synthesis ◽  
Lewis Acid ◽  
Alder Reaction ◽  
Diels Alder ◽  
Asymmetric Total Synthesis ◽  
Diels Alder Reaction

Total synthesis of the complex taxane diterpene canataxpropellane

Science ◽  
2020 ◽  
Vol 367 (6478) ◽  
pp. 676-681 ◽  
Author(s):  
Fabian Schneider ◽  
Konstantin Samarin ◽  
Simone Zanella ◽  
Tanja Gaich
Keyword(s):  
Total Synthesis ◽  
Anticancer Agent ◽  
Alder Reaction ◽  
Diels Alder ◽  
Core Structure ◽  
Natural Sources ◽  
The Core ◽  
Diels Alder Reaction ◽  
Cyclobutane Ring ◽  
Quaternary Carbons

Canataxpropellane belongs to the medicinally important taxane diterpene family. The most prominent congener, Taxol, is one of the most commonly used anticancer agent in clinics today. Canataxpropellane exhibits a taxane skeleton with three additional transannular C–C bonds, resulting in a total of six contiguous quaternary carbons, of which four are located on a cyclobutane ring. Unfortunately, isolation of canataxpropellane from natural sources is inefficient. Here, we report a total synthesis of (–)-canataxpropellane in 26 steps and 0.5% overall yield from a known intermediate corresponding to 29 steps from commercial material. The core structure of the (–)-canataxpropellane (2) was assembled in two steps using a Diels–Alder/ortho-alkene-arene photocycloaddition sequence. Enantioselectivity was introduced by designing chiral siloxanes to serve as auxiliaries in the Diels–Alder reaction.

scholarly journals Divergent Asymmetric Total Synthesis of All Four Pestalotin Diastereomers from (R)-Glycidol

Molecules ◽  
2020 ◽  
Vol 25 (2) ◽  
pp. 394 ◽  
Author(s):  
Mizuki Moriyama ◽  
Kohei Nakata ◽  
Tetsuya Fujiwara ◽  
Yoo Tanabe
Keyword(s):  
Total Synthesis ◽  
Lewis Acids ◽  
Alder Reaction ◽  
Diels Alder ◽  
Aldol Reactions ◽  
Asymmetric Total Synthesis ◽  
High Chemical ◽  
Diels Alder Reaction ◽  
Mukaiyama Aldol ◽  
Optical Rotations

All four chiral pestalotin diastereomers were synthesized in a straightforward and divergent manner from common (R)-glycidol. Catalytic asymmetric Mukaiyama aldol reactions of readily-available bis(TMSO)diene (Chan’s diene) with (S)-2-benzyloxyhexanal derived from (R)-glycidol produced a syn-aldol adduct with high diastereoselectivity and enantioselectivity using a Ti(iOPr)4/(S)-BINOL/LiCl catalyst. Diastereoselective Mukaiyama aldol reactions mediated by catalytic achiral Lewis acids directly produced not only a (1′S,6S)-pyrone precursor via the syn-aldol adduct using TiCl4, but also (1′S,6R)-pyrone precursor via the antialdol adduct using ZrCl4, in a stereocomplementary manner. A Hetero-Diels-Alder reaction of similarly available mono(TMSO)diene (Brassard’s diene) with (S)-2-benzyloxyhexanal produced the (1′S,6S)-pyrone precursor promoted by Eu(fod)3 and the (1′S,6R)-pyrone precursor Et2AlCl. Debenzylation of the (1′S,6S)-precursor and the (1′S,6R)-precursor furnished natural (−)-pestalotin (99% ee, 7 steps) and unnatural (+)-epipestalotin (99% ee, 7 steps), respectively. Mitsunobu inversions of the obtained (−)-pestalotin and (+)-epipestalotin successfully produced the unnatural (+)-pestalotin (99% ee, 9 steps) and (−)-epipestalotin (99% ee, 9 steps), respectively, in a divergent manner. All four of the obtained chiral pestalotin diastereomers possessed high chemical and optical purities (optical rotations, 1H-NMR, 13C-NMR, and HPLC measurements).

Asymmetric Total Synthesis of Caribenol A via an Intramolecular Diels–Alder Reaction

2013 ◽  
Vol 78 (11) ◽  
pp. 5492-5504 ◽  
Author(s):  
Jing-Chun Han ◽  
Lian-Zhu Liu ◽  
Yuan-Yuan Chang ◽  
Guo-Zong Yue ◽  
Jie Guo ◽  
...  
Keyword(s):  
Total Synthesis ◽  
Alder Reaction ◽  
Diels Alder ◽  
Asymmetric Total Synthesis ◽  
Diels Alder Reaction

Total synthesis of (−)-depyranoversicolamide B

2015 ◽  
Vol 51 (89) ◽  
pp. 16143-16146 ◽  
Author(s):  
Wen-Fang Qin ◽  
T. Xiao ◽  
D. Zhang ◽  
Lin-Feng Deng ◽  
Y. Wang ◽  
...  
Keyword(s):  
Total Synthesis ◽  
Ring Opening ◽  
Alder Reaction ◽  
Diels Alder ◽  
Asymmetric Total Synthesis ◽  
Diels Alder Reaction ◽  
Key Steps

Asymmetric total synthesis of (−)-depyranoversicolamide B (12) is described from easily prepared chiral pyrroloindoline 21. Key steps in the synthesis are reductive ring opening of the pyrrolo ring in 21 and stereoselective intramolecular Diels–Alder reaction of 18.

Synthesis of myxobacteria metabolites

2012 ◽  
Vol 84 (6) ◽  
pp. 1421-1433 ◽  
Author(s):  
Stephen L. Birkett ◽  
Darran A. Loits ◽  
Samantha Wimala ◽  
Mark A. Rizzacasa
Keyword(s):  
Total Synthesis ◽  
Biological Activities ◽  
Aldol Reaction ◽  
Alder Reaction ◽  
Diels Alder ◽  
Sonogashira Coupling ◽  
Partial Reduction ◽  
Diels Alder Reaction ◽  
Apicularen A ◽  
Excellent Source

Myxobacteria are an excellent source of novel secondary metabolites with a range of biological activities. This review details the synthesis of several examples of these natural products. The total synthesis of all the members of the crocacin family is presented where the stereochemistry of the stereotetrad was set via a tin-mediated syn-aldol reaction followed by selective anti-reduction. The other key step in the route to crocacins A, B, and D was the introduction of the enamide functionality by acylation of an enecarbamate. A formal synthesis of apicularen A is also discussed, which involved a base-induced macrolactonization reaction and a transannular oxy-Michael cyclization to secure the tetrahydropyran ring. Finally, the total synthesis of deshydroxyajudazol B is summarized. This route details a modified approach to the 2,4-disubstituted oxazole, and a Diels–Alder reaction followed by aromatization was utilized to form the isochromanone moiety. A highly efficient Sonogashira coupling followed by partial reduction then gave deshydroxyajudazol B.

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