Unusual KIE and dynamics effects in the Fe-catalyzed hetero-Diels-Alder reaction of unactivated aldehydes and dienes DOI Creative Commons
Yuhong Yang, Xiaoyong Zhang, Liping Zhong

et al.

Nature Communications, Journal Year: 2020, Volume and Issue: 11(1)

Published: April 15, 2020

Abstract Hetero-Diels-Alder (HDA) reaction is an important synthetic method for many natural products. An iron(III) catalyst was developed to catalyze the challenging HDA of unactivated aldehydes and dienes with high selectivity. Here we report extensive density-functional theory (DFT) calculations molecular dynamics simulations that show effects iron (including its coordinate mode and/or spin state) on this reaction: considerably enhancing dynamically stepwise process, broadening entrance channel narrowing exit from concerted asynchronous transition states. Also, our combined computational experimental secondary KIE studies reveal unexpectedly large values five-coordinate pathway even considerable C–C bond forming, due equilibrium isotope effect change in metal coordination. Moreover, steric electronic are computationally shown dictate C=O chemoselectivity α,β-unsaturated aldehyde, which verified experimentally. Our mechanistic study may help design homogeneous, heterogeneous biological catalysts reaction.

Language: Английский

Cytochrome P450 enzymes in fungal natural product biosynthesis DOI
Xingwang Zhang, Jiawei Guo, Fangyuan Cheng

et al.

Natural Product Reports, Journal Year: 2021, Volume and Issue: 38(6), P. 1072 - 1099

Published: Jan. 1, 2021

P450s play crucial roles in fungal natural product biosynthesis by mediating various common and uncommon reactions.

Language: Английский

Citations

141

Functional supramolecular systems: design and applications DOI
И. С. Антипин,

М. В. Алфимов,

V. V. Arslanov

et al.

Russian Chemical Reviews, Journal Year: 2021, Volume and Issue: 90(8), P. 895 - 1107

Published: April 20, 2021

The interest in functional supramolecular systems for the design of innovative materials and technologies, able to fundamentally change world, is growing at a high pace. huge array publications that appeared recent years global literature calls systematization structural trends inherent formation these revealed different molecular platforms practically useful properties they exhibit. attention concentrated on topics related are actively explored institutes universities Russia last 10–15 years, such as chemistry host–guest complexes, crystal engineering, self-assembly self-organization solutions interfaces, biomimetics machines devices. bibliography includes 1714 references.

Language: Английский

Citations

120

Biosynthesis of fungal terpenoids DOI
Pan Luo,

Jia-Hua Huang,

Jian‐Ming Lv

et al.

Natural Product Reports, Journal Year: 2024, Volume and Issue: 41(5), P. 748 - 783

Published: Jan. 1, 2024

This review covers all fungal terpenoid cyclases (TCs), including class I and II TCs as well emerging UbiA-type TCs, together with their tailoring enzymes, focusing on newly identified enzymes from 2015 to August 2023.

Language: Английский

Citations

36

Designer “Quasi-Benzyne”: The Spontaneous Reduction of Ortho-Diiodotetrafluorobenzene on Water Microdroplets DOI
Huan Chen,

Ruijing Wang,

Tatsuya Chiba

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(15), P. 10979 - 10983

Published: April 8, 2024

It has been widely shown that water microdroplets have a plethora of unique properties are highly distinct from those bulk water, among which an especially intriguing one is the strong reducing power as result electrons spontaneously generated at air–water interface. In this study, we take advantage to reduce ortho-diiodotetrafluorobenzene (o-C6F4I2) into C6F4I2•– radical anion. Photoelectron spectroscopy and density functional theory computations reveal excess electron in occupies I–C1–C2–I linkage, elongates C–I bonds but surprisingly shortens C1–C2 bond, making bond order higher than double similar benzyne molecule, so named it "quasi-benzyne". The anion was further successfully utilized Diels–Alder reaction, typical reaction for benzyne. This study provides good example strategically utilizing spontaneous generating exotic anion, anticipate microdroplet chemistry can be avenue rich opportunities new catalyst-free organic reactions.

Language: Английский

Citations

18

FAD-dependent enzyme-catalysed intermolecular [4+2] cycloaddition in natural product biosynthesis DOI
Lei Gao, Cong Su,

Xiaoxia Du

et al.

Nature Chemistry, Journal Year: 2020, Volume and Issue: 12(7), P. 620 - 628

Published: May 25, 2020

Language: Английский

Citations

133

Enzymatic dimerization in the biosynthetic pathway of microbial natural products DOI
Jia-Wang Liu, Anan Liu, Youcai Hu

et al.

Natural Product Reports, Journal Year: 2021, Volume and Issue: 38(8), P. 1469 - 1505

Published: Jan. 1, 2021

Cytochrome P450s, laccases, and intermolecular [4 + 2] cyclases, along with other enzymes were utilized to catalyze varied dimerization of matured natural products so as create the structural diversity complexity in microorganisms.

Language: Английский

Citations

61

Deciphering chemical logic of fungal natural product biosynthesis through heterologous expression and genome mining DOI
Chen‐Yu Chiang, M. Ohashi, Yi Tang

et al.

Natural Product Reports, Journal Year: 2022, Volume and Issue: 40(1), P. 89 - 127

Published: Sept. 20, 2022

Covering: 2010 to 2022Heterologous expression of natural product biosynthetic gene clusters (BGCs) has become a widely used tool for genome mining cryptic pathways, bottom-up investigation enzymes, and engineered biosynthesis new variants. In the field fungal products, heterologous complete pathway was first demonstrated in tenellin

Language: Английский

Citations

48

A cyclase that catalyses competing 2 + 2 and 4 + 2 cycloadditions DOI
Hongbo Wang, Yike Zou, Miao Li

et al.

Nature Chemistry, Journal Year: 2023, Volume and Issue: 15(2), P. 177 - 184

Published: Jan. 23, 2023

Language: Английский

Citations

28

Sorbremnoids A and B: NLRP3 Inflammasome Inhibitors Discovered from Spatially Restricted Crosstalk of Biosynthetic Pathways DOI

Kaijin Zhang,

Junyu Liu, Yuqi Jiang

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(26), P. 18172 - 18183

Published: June 18, 2024

Crosstalk-oriented chemical evolution of natural products (NPs) is an efficacious strategy for generating novel skeletons through coupling reactions between NP fragments. In this study, two NOD-like receptor protein 3 (NLRP3) inflammasome inhibitors, sorbremnoids A and B (1 2), with unprecedented architectures were identified from a fungus Penicillium citrinum. Compounds 1 2 exemplify rare instances hybrid NPs formed via major facilitator superfamily (MFS)-like enzyme by reactive intermediates separate biosynthetic gene clusters (BGCs), pcisor pci56. Both are NLRP3 inhibitors. Sorbremnoid demonstrated strong inhibition IL-1β directly binding to the protein, inhibiting assembly activation in vitro, potential application diabetic refractory wound healing suppression excessive inflammatory responses. This research will inspire development anti-NLRP3 agents as lead treatments enhance knowledge pertaining derived crosstalk.

Language: Английский

Citations

12

An enzymatic Alder-ene reaction DOI
M. Ohashi, Cooper S. Jamieson,

Yujuan Cai

et al.

Nature, Journal Year: 2020, Volume and Issue: 586(7827), P. 64 - 69

Published: Sept. 30, 2020

Language: Английский

Citations

56