The First Synthesis of Herbicidin B. Stereoselective Construction of the Tricyclic Undecose Moiety by a Conformational Restriction Strategy Using Steric Repulsion between Adjacent Bulky Silyl Protecting Groups on a Pyranose Ring

Ichikawa, Satoshi; Shuto, and Satoshi; Matsuda, Akira

doi:10.1021/ja992608h

Cited by 85 publications

(46 citation statements)

References 26 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Only moderate selectivity was achieved in each case (E/Z ratio ranging from 65:45 to 80:20), which indicated that remote control could not be achieved perfectly with the anti-conformer containing the rigid amine moiety. These reaction results as well as the transmission information between the silicon and amine centers, which are impacted by the rotation-controllable architecture of atropisomeric amides, also provide a chemical model of allostery and might be useful in the description of steric repulsion-directed reaction mechanism [15] and working models of molecular rotors/motors. [16] Although the synthesis of secondary amine-and tertiary amide-containing alkenes was not satisfactory with regard to E/Z selectivity, to our knowledge, desilylation-olefination has not been reported so far for the construction of such substituted olefins; especially in the case of the alcohol-containing atropisomeric amide 4, this scheme provides pure (E)-product in moderate to good yields.…”

Section: Resultsmentioning

confidence: 99%

Silicon‐Based Bulky Group‐Induced Remote Control and Conformational Preference in the Synthesis and Application of Isolable Atropisomeric Amides with Secondary Alcohol or Amine Moieties

Bai

Deng

et al. 2014

Chemistry An Asian Journal

View full text Add to dashboard Cite

Remote stereocontrol through conformational transmission along a carbon chain is highly important in synthetic systems and molecular architectures. In this work, the interactional reactivity between a remote silicon-based bulky group and an O-/N-containing functional group has been revealed and determined by lateral lithiation-substitution, desilylation, as well as desilylation-olefination with benzaldehyde. The results suggest considerable information transmission and steric hindrance that can be exploited for the controllable synthesis of atropisomeric molecules. Based on the remote steric effect of a functional group across the aromatic ring of an amide, the construction of isolable atropisomeric amides with functional groups, such as alcohol, amine, and olefin was successfully achieved. All these new atropisomers were obtained in reasonable yield in pure diastereomeric form, and the specific configuration of representative products was confirmed by X-ray crystallography.

show abstract

Section: Resultsmentioning

confidence: 99%

Silicon‐Based Bulky Group‐Induced Remote Control and Conformational Preference in the Synthesis and Application of Isolable Atropisomeric Amides with Secondary Alcohol or Amine Moieties

Bai

Deng

et al. 2014

Chemistry An Asian Journal

View full text Add to dashboard Cite

show abstract

“…Chemie the opposite or an unusual conformer, [255] in which most substituents have an axial orientation as a result of steric repulsion between the bulky protecting groups. Furthermore, glycosidation of the silyl-protected donors often gave preferentially or exclusively one stereoisomer, even without neighboring-group participation.…”

Section: Methodsmentioning

confidence: 99%

New Principles for Glycoside‐Bond Formation

2009

View full text Add to dashboard Cite

Increased understanding of the important roles that oligosaccharides and glycoconjugates play in biological processes has led to a demand for significant amounts of these materials for biological, medicinal, and pharmacological studies. Therefore, tremendous effort has been made to develop new procedures for the synthesis of glycosides, whereby the main focus is often the formation of the glycosidic bonds. Accordingly, quite a few review articles have been published over the past few years on glycoside synthesis; however, most are confined to either a specific type of glycoside or a specific strategy for glycoside synthesis. In this Review, new principles for the formation of glycoside bonds are discussed. Developments, mainly in the last ten years, that have led to significant advances in oligosaccharide and glycoconjugate synthesis have been compiled and are evaluated.

show abstract

“…The HHDP group of 12 would be constructed by oxidative intramolecular coupling of gallates, each middle hydroxy group of which was protected by a benzyl group, on the 3‐ and 4‐positions of the glucopyranose ring as in 14 . These positions are distinguishable from the other hydroxy groups of glucose through the use of the 3,4‐ O ‐tetraisopropyldisiloxanilidene‐protected glucose derivative 6 , which is a known compound 9. Therefore, we began the synthesis with 2,6‐acylation of 6 by partly allylated galloyl donors.…”

Section: Resultsmentioning

confidence: 99%

Total Synthesis of Cercidinin A

2013

View full text Add to dashboard Cite

An ellagitannin, cercidinin A, was synthesized through both intramolecular coupling of gallates on a glucose moiety and double esterification of protected hexahydroxydiphenic acid to a diol. The total synthesis confirmed the revised structure of cercidinin A as 1,2,6‐tri‐O‐galloyl‐3,4‐(R)‐hexahydroxydiphenoyl (HHDP) β‐D‐glucose. This is the first synthesis of 3,4‐HHDP‐bridged ellagitannins and was achieved after overcoming two challenges: (1) full galloylation of β‐glucose hindered the formation of the 3,4‐HHDP group, and (2) the fully benzylated galloyl group, which is a routine component in ellagitannin synthesis, was not always appropriate. The solutions to these problems can be used to form a strategy for the synthesis of complex ellagitannins.

show abstract

The First Synthesis of Herbicidin B. Stereoselective Construction of the Tricyclic Undecose Moiety by a Conformational Restriction Strategy Using Steric Repulsion between Adjacent Bulky Silyl Protecting Groups on a Pyranose Ring

Cited by 85 publications

References 26 publications

Silicon‐Based Bulky Group‐Induced Remote Control and Conformational Preference in the Synthesis and Application of Isolable Atropisomeric Amides with Secondary Alcohol or Amine Moieties

Silicon‐Based Bulky Group‐Induced Remote Control and Conformational Preference in the Synthesis and Application of Isolable Atropisomeric Amides with Secondary Alcohol or Amine Moieties

New Principles for Glycoside‐Bond Formation

Total Synthesis of Cercidinin A

Contact Info

Product

Resources

About