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

Li, Tianze; Geng, Chang‐An; Yin, Xiu-Juan; Yang, Tonghua; Chen, Xing‐Long; Huang, Xiaoyan; Ma, Yun‐Bao; Zhang, Xuemei; Chen, Ji-Jun

doi:10.1021/acs.orglett.6b03801

Cited by 34 publications

(13 citation statements)

References 16 publications

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“…Chen group reported the first catalytic asymmetric total synthesis of (+)‐ and (−)‐paeoveitol via a biomimetic hetero‐Diels–Alder reaction with chiral SPA 3 (Scheme 98). [ 102 ] The key feature of the total synthesis is the chiral SPA‐catalyzed asymmetric hetero‐ Diels−Alder reaction of paeoveitol D and O‐quinone methoide to provide the excellent diastereo‐ and enantioselectivity (>99 : 1 dr and 90% ee) and synthesize both paeoveitol enantiomers from the same substrates by simply changing the catalyst's stereochemistry.…”

Section: Application In Total Synthesismentioning

confidence: 99%

Chiral Spirocyclic Phosphoric Acids and Their Growing Applications

et al. 2021

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What is the most favorite and original chemistry developed in your research group? Developing SPINOL-phosphoric acids (SPAs), TM-SPINOL-phosphoric acids (SPAs 2.0) and PCP-derived planar chiral phosphoric acids (PPAs) for asymmetric catalysis. What is the most important personality for scientific research? Curiosity, optimism, self-confidence and persistence. What's your hobbies? What's your favorite book(s)? I enjoy cooking. My favorite book is Journey to the West. Who influences you mostly in your life? My mother. What is your favorite journal(s)? The journals publishing the original and systematic work of synthetic chemistry. Could you please give us some advices on improving Chinese Journal of Chemistry? Fast review, fast publication, fast promotion via new media.

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Section: Application In Total Synthesismentioning

confidence: 99%

Chiral Spirocyclic Phosphoric Acids and Their Growing Applications

et al. 2021

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“…Paeoveitol is one of the main antipsychotic components of Radix Paeoniae Rubra. [30][31] In 2017, Chen Jijun's group reported for the first time the enantioselective 6-step total synthesis of Paeoveitol with an overall yield of 42% [32], and the best result was the 7-step total synthesis published by Xie Zhixiang's group with an overall yield of 26% [33]. SPA catalyzed hetero Diels alter reaction, as a key step, provides high yield (up to 95%) and good corresponding selectivity (up to 90% ee).…”

Section: Introductionmentioning

confidence: 99%

Applications of chiral spirocyclic phosphoric acid in the synthesis of natural products

Yang

2021

E3S Web Conf.

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With a 10 years development, chiral spirocyclic phosphoric acids (SPAs) have attracted a substantial amount of attention from the synthetic organic chemistry community. This kind of small molecule organic catalysts has some advantages like easy to obtain, no transition metal and wide application range. Because of avoiding the use of toxic substances which are limited in the process of drug synthesis, a large number of studies pay attention to the key structures (such as indole, carbozole.) containing pharmacological active components in natural products. And most of them get a excellent result in yields (more than 80% yield) and enantioselectivities (more than 90% ee). These studies can provide new pathways to nature products.

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“…[12] Furthermore, QMs also react with electron-rich alkenes in the Diels-Alder reaction and give chromane products, [5] and this techniquew as recently exploitedi nt he synthesis of complex molecular structures. [13][14][15][16][17][18] Particularly importanti st he reactivity of QMs with biologically relevantn ucleophilesi ncluding amino acids, [19] proteins, [20,21] nucleobases [22] and DNA, [23][24][25][26] and G-quadruplex structures. [27][28][29][30] Moreover,R okita et al demonstrated that QMs reacteda sr eversible DNA cross-linking DNA agents, [31][32][33] which was connected to the biological action of some anticancer antibiotics such as mitomycine.…”

Section: Introductionmentioning

confidence: 99%

“…Electrophiles (e.g., H + ) attack the carbonyl oxygen atom, whereas the exocyclic methylene position is prone to attack by nucleophiles that in a Michael addition react with QMs . Furthermore, QMs also react with electron‐rich alkenes in the Diels–Alder reaction and give chromane products, and this technique was recently exploited in the synthesis of complex molecular structures . Particularly important is the reactivity of QMs with biologically relevant nucleophiles including amino acids, proteins, nucleobases and DNA, and G‐quadruplex structures .…”

Section: Introductionmentioning

confidence: 99%

Ultrafast Adiabatic Photodehydration of 2‐Hydroxymethylphenol and the Formation of Quinone Methide

Škalamera

Antol

Mlinarić‐Majerski

et al. 2018

Chemistry A European J

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The photochemical reactivity of 2-hydroxymethylphenol (1) was investigated experimentally by photochemistry under cryogenic conditions, by detecting reactive intermediates by IR spectroscopy, and by using nanosecond and femtosecond transient absorption spectroscopic methods in solution at room temperature. In addition, theoretical studies were performed to facilitate the interpretation of the experimental results and also to simulate the reaction pathway to obtain a better understanding of the reaction mechanism. The main finding of this work is that photodehydration of 1 takes place in an ultrafast adiabatic photochemical reaction without any clear intermediate, delivering quinone methide (QM) in the excited state. Upon photoexcitation to a higher vibrational level of the singlet excited state, 1 undergoes vibrational relaxation leading to two photochemical pathways, one by which synchronous elimination of H O gives QM 2 in its S state and the other by which homolytic cleavage of the phenolic O-H bond produces a phenoxyl radical (S ). Both are ultrafast processes that occur within a picosecond. The excited state of QM 2 (S ) probably deactivates to S through a conical intersection to give QM 2 (S ), which subsequently delivers benzoxete 4. Elucidation of the reaction mechanisms for the photodehydration of phenols by which QMs are formed is important to tune the reactivity of QMs with DNA and proteins for the potential application of QMs in medicine as therapeutic agents.

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

Cited by 34 publications

References 16 publications

Chiral Spirocyclic Phosphoric Acids and Their Growing Applications

Chiral Spirocyclic Phosphoric Acids and Their Growing Applications

Applications of chiral spirocyclic phosphoric acid in the synthesis of natural products

Ultrafast Adiabatic Photodehydration of 2‐Hydroxymethylphenol and the Formation of Quinone Methide

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