A highly efficient synthesis of the DEFG-ring system of rubriflordilactone B

Wang, Yong; Zhang, Yuhan; Li, Zhongle; Zhang, Yang; Xie, Zhenzhen

doi:10.1039/c6qo00241b

Cited by 11 publications

(4 citation statements)

References 31 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Paucifloral F ( 5 ), a trans -2,3-diaryl-1-indanone secondary metabolite, was reportedly isolated from the stem bark of Vatica pauciflora . In addition, daphenylline as well as rubriflordilactones A and B are complex natural products containing indane as their core. , …”

Section: Introductionmentioning

confidence: 99%

Selective Divergent Synthesis of Indanols, Indanones, and Indenes via Acid-Mediated Cyclization of (Z)- and (E)-(2-Stilbenyl)methanols and Its Application for the Synthesis of Paucifloral F Derivatives

et al. 2018

View full text Add to dashboard Cite

Starting from bromo/iodobenzaldehyde derivatives, the corresponding (Z)- and (E)-(2-stilbenyl)methanols could be prepared in 2–5 steps via Pd-catalyzed cross-coupling reactions (Sonogashira and Heck reactions) followed by aryllithium/aryl Grignard addition. For the (E)-stilbenes, subsequent acid-mediated cyclization using p-TsOH immobilized on silica (PTS-Si) at low temperatures furnished the 2,3-trans-1-indanols with complete stereocontrol at the C2–C3. Further oxidization of the alcohol provided the indanones, which are structurally related to the natural product paucifloral F. At higher temperatures, 1,2- and 2,3-disubstituted indenes could be selectively prepared in good to excellent yields. On the other hand, the (Z)-stilbenes, under similar conditions (PTS-Si), did not give the indanols; only the 1,2-disubstituted indenes could be obtained. To gain further insights into the stereochemistry at C2–C3 for the (Z)-stilbenes, hydride or azide was employed as a nucleophile; the corresponding indane products were obtained with the cis stereochemistry at the C2–C3. Thus, the (Z)- or (E)-olefin geometry of the substrate directed the stereoselective indanyl cyclization to furnish the cis or trans at the C2–C3 ring junction, respectively, while reaction conditions controlled the selectivity of the product types.

show abstract

Section: Introductionmentioning

confidence: 99%

Selective Divergent Synthesis of Indanols, Indanones, and Indenes via Acid-Mediated Cyclization of (Z)- and (E)-(2-Stilbenyl)methanols and Its Application for the Synthesis of Paucifloral F Derivatives

et al. 2018

View full text Add to dashboard Cite

show abstract

“…A handful of syntheses of other congeners have been achieved since then, by the groups of Yang, Li, Anderson, Tang, and Ding, respectively. A series of synthetically useful strategies and methods have been developed in the related studies. − …”

Section: Introductionmentioning

confidence: 99%

Elucidation of the Structure of Pseudorubriflordilactone B by Chemical Synthesis

Yang

Sun

et al. 2019

J. Am. Chem. Soc.

View full text Add to dashboard Cite

Rubriflordilactone B (1) is a schinortriterpenoid isolated by Sun and colleagues, which possesses a tetrasubstituted benzene moiety and eight stereocenters. The previous synthesis of 1 by Li and co-workers uncovered the existence of its naturally occurring stereoisomer “pseudorubriflordilactone B”. Here we report a collaborative study by the two groups that elucidates the structure of pseudorubriflordilactone B to be 16,17-bis-epi-rubriflordilactone B (26). Chemical synthesis served as an important tool in the structure determination. Taking advantage of a modular synthetic route, we systematically “mutated” the configurations of C-23, C-22, C-20, and C-16/C-17 located at the right-hand domain of 1, and thus prepared its 15 stereoisomers for spectrum comparison. The 1H NMR spectra of synthetic 26 in deuterated chloroform and pyridine were identical to those of authentic pseudorubriflordilactone B, respectively. This synthetic sample displayed anti-HIV activity (EC50 = 0.288 μM) in vitro.

show abstract

“…The synthetic challenge posed by their intricate structures containing multichiral centers and high-level oxidation states is formidable and has aroused intensive efforts to achieve the total synthesis of the Schisandra triterpenoids since Yang and co-workers pioneered the total synthesis of the schindilactone A ( 1 ) . So far, two completed syntheses of rubriflordilactone A ( 3 ) have been disclosed. ,, The first total synthesis by Li and co-workers featured a 6π-electrocyclization/aromatization sequence to assemble the penta-substituted arene in 2014 . Utilizing either a palladium-catalyzed bromoendiyne cyclization or a cobalt-catalyzed alkyne cyclotrimerization as the key transformation, Anderson and co-workers accomplished the second total synthesis to rubriflordilactone A ( 3 ) in 2015 .…”

mentioning

confidence: 99%

Total Synthesis of (±)-Rubriflordilactone A

Zheng,

Guo,

Wang

et al. 2024

J. Am. Chem. Soc.

View full text Add to dashboard Cite

A new and efficient synthesis of rubriflordilactone A has been realized. The key transformations include the following:(1) an intramolecular Prins cyclization to establish the seven-membered ring containing two contiguous stereocenters; (2) a Mukaiyama hydration/oxa-Michael cascade to construct the B-ring; and (3) an unprecedented stereocontrol intermolecular o-QM type [4 + 2]-cycloaddition to rapidly assemble core structure of rubriflordilactone A.

show abstract

A highly efficient synthesis of the DEFG-ring system of rubriflordilactone B

Abstract: A highly efficient synthesis of the DEFG-ring system of rubriflordilactone B via polar-radical-crossover cycloaddition and carbonyl allylation/lactonization is described.

Cited by 11 publications

References 31 publications

Selective Divergent Synthesis of Indanols, Indanones, and Indenes via Acid-Mediated Cyclization of (Z)- and (E)-(2-Stilbenyl)methanols and Its Application for the Synthesis of Paucifloral F Derivatives

Selective Divergent Synthesis of Indanols, Indanones, and Indenes via Acid-Mediated Cyclization of (Z)- and (E)-(2-Stilbenyl)methanols and Its Application for the Synthesis of Paucifloral F Derivatives

Elucidation of the Structure of Pseudorubriflordilactone B by Chemical Synthesis

Total Synthesis of (±)-Rubriflordilactone A

Contact Info

Product

Resources

About