Catalytic asymmetric synthesis of (−)-E-δ-viniferin via an intramolecular C–H insertion of diaryldiazomethane using Rh2(S-TFPTTL)4

Stilbenes are a small family of polyphenolic secondary metabolites that can be found in several distantly related plant species. These compounds act as phytoalexins, playing a crucial role in plant defense against phytopathogens, as well as being involved in the adaptation of plants to abiotic environmental factors. Among stilbenes, trans-resveratrol is certainly the most popular and extensively studied for its health properties. In recent years, an increasing number of stilbene compounds were subjected to investigations concerning their bioactivity. This review presents the most updated knowledge of the stilbene biosynthetic pathway, also focusing on the role of several environmental factors in eliciting stilbenes biosynthesis. The effects of ultraviolet radiation, visible light, ultrasonication, mechanical stress, salt stress, drought, temperature, ozone, and biotic stress are reviewed in the context of enhancing stilbene biosynthesis, both in planta and in plant cell and organ cultures. This knowledge may shed some light on stilbene biological roles and represents a useful tool to increase the accumulation of these valuable compounds.

show abstract

“…In recent years, considerable efforts have also been made to develop non-enzymatic methods to produce oligostilbenes [179,180].…”

Section: Oligomerizationmentioning

confidence: 99%

Impact of Environmental Factors on Stilbene Biosynthesis

Valletta

Iozia

Leonelli

2021

Plants

115

View full text Add to dashboard Cite

show abstract

“…Although initial reactions with achiral rhodium complexes showed nominal reactivity and diastereoselectivity, the use of catalyst 17 improved both the yield and diastereoselectivity while also enabling high degrees of enantioselectivity (Table 1, entry 3). This method was used as the key bond construction for our synthesis of E ‐δ‐viniferin, representing the first enantioselective synthesis of an oligoresveratrol natural product [52, 53] . Subsequent studies elucidated the origins of byproducts and computed transition state structures that explain the catalyst control of stereochemistry [36] .…”

Section: C−h Insertionmentioning

confidence: 99%

Transition Metal Catalyzed Insertion Reactions with Donor/Donor Carbenes

et al. 2020

View full text Add to dashboard Cite

Donor/donor carbenes are relatively new in the field of carbene chemistry; although applications in C−H and X−H insertion reactions are few in number, they demonstrate exquisite chemo‐ and stereo‐selectivity. Recent reports have shown that C−H, N−H, B−H, O−H, S−H, Si−H, Ge−H, Sn−H and P−H insertion reactions are feasible with a variety of transition metal catalysts, both inter‐ and intramolecularly. Furthermore, high degrees of diastereo‐ and enantioselectivity have been observed in several cases. Methods typically involve the formation of a diazo‐based carbene precursor, but procedures using diazo‐free metal carbenes have been developed with significant success. This Minireview covers transition‐metal catalyzed insertion reactions with donor/donor and donor carbenes, providing context for future developments in this emerging field.

show abstract

“…In 2015, Hasimoto and co-workers reported a second asymmetric synthesis of (E)--viniferin in 8 steps and 27% overall yield starting from commercially available 5-bromosalicylaldehyde, 98 and utilizing a slightly different catalyst, [Rh 2 (S-TFPTTL) 4 ], as an efficient catalyst for the intramolecular C-H insertion reaction of the aryl[5-bromo-2-(4methoxybenzyloxy)phenyl]diazomethane derivative to obtain the key bromo intermediate with perfect cis diastereoselectivity in 96% ee, which was easily elaborated to obtain the final (E)--viniferin (Scheme 32).…”

Section: Review Syn Thesismentioning

confidence: 99%

Recent Advances in Synthetic Strategies to 2,3-Dihydrobenzofurans

Laurita

D’Orsi²,

Chiummiento³

et al. 2020

Synthesis

View full text Add to dashboard Cite

This review gives an overview on recent developments in methods for the construction of compounds with the 2,3-dihydrobenzofuran core in the period 2012 to 2019. Interest in 2,3-dihydrobenzofurans is constantly increasing. The methods are divided into intermolecular and intramolecular approaches. Intermolecular approaches are subdivided according to the parent intermediate for the key reaction, while intermolecular approaches are subdivided according by which bond is formed in the key reaction. The transformation of benzofurans to dihydrobenzofurans and other miscellaneous methods are also discussed. Approaches useful for the synthesis of natural products are emphasized.1 Introduction2 Intermolecular Approaches2.1 o-Quinone Methides and o-Quinones2.2 p-Quinone Methides and p-Quinones2.3 Nitrogen-Containing Phenols and Quinones2.4 o-Hydroxyphenylcarbonyl Derivatives and Phenols2.5 Miscellaneous3 Intramolecular Approaches3.1 O–C2 Bond Forming3.2 C2–C3 Bond Forming3.3 C3–Aryl Bond Forming3.4 O–Aryl Bond Forming4 From BF to DHB5 Rearrangements and Aromatizations

show abstract

Catalytic asymmetric synthesis of (−)-E-δ-viniferin via an intramolecular C–H insertion of diaryldiazomethane using Rh2(S-TFPTTL)4

Cited by 34 publications

References 71 publications

Impact of Environmental Factors on Stilbene Biosynthesis

Impact of Environmental Factors on Stilbene Biosynthesis

Transition Metal Catalyzed Insertion Reactions with Donor/Donor Carbenes

Recent Advances in Synthetic Strategies to 2,3-Dihydrobenzofurans

Contact Info

Product

Resources

About