Exploring Structure–Function Relationships of Aryl Pyrrolidine-Based Hydrogen-Bond Donors in Asymmetric Catalysis Using Data-Driven Techniques DOI
Mohammad H. Samha, Julie L. Hofstra Wahlman, Jacquelyne A. Read

et al.

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(24), P. 14836 - 14845

Published: Nov. 22, 2022

Hydrogen bond-based organocatalysts rely on networks of attractive noncovalent interactions (NCIs) to impart enantioselectivity. As a specific example, aryl pyrrolidine substituted urea, thiourea, and squaramide function cooperatively through hydrogen bonding difficult-to-predict NCIs as the reaction partners. To uncover synergistic effect structural components this catalyst class, we applied data science tools study various model reactions using derivatized, pyrrolidine-based, hydrogen-bond donor (HBD) library. Through combination experimentally collected mined from previous reports, statistical models were constructed, illuminating general features necessary for high A distinct dependence identity electrophilic partner HBD is observed, suggesting that interaction conserved throughout analyzed. The resulting also demonstrate predictive capability by successful improvement previously reported out-of-sample components. Overall, highlights power in exploring mechanistic hypotheses asymmetric catalysis provides prediction platform applicable future optimization.

Language: Английский

Stereoselective Synthesis of Cyclobutanes by Contraction of Pyrrolidines DOI Creative Commons

Chunngai Hui,

Lukas Brieger, Carsten Strohmann

et al.

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(45), P. 18864 - 18870

Published: Nov. 8, 2021

Here we report a contractive synthesis of multisubstituted cyclobutanes containing multiple stereocenters from readily accessible pyrrolidines using iodonitrene chemistry. Mediated by nitrogen extrusion process, the stereospecific involves radical pathway. Unprecedented unsymmetrical spirocyclobutanes were prepared successfully, and concise, formal cytotoxic natural product piperarborenine B is reported.

Language: Английский

Citations

116
Progress in organocatalysis with hypervalent iodine catalysts DOI Creative Commons
Fateh V. Singh,

Samata E. Shetgaonkar,

Manjula Krishnan

et al.

Chemical Society Reviews, Journal Year: 2022, Volume and Issue: 51(18), P. 8102 - 8139

Published: Jan. 1, 2022

Hypervalent iodine compounds as environmentally friendly and relatively inexpensive reagents have properties similar to transition metals. They are employed alternatives metal catalysts in organic synthesis mild, nontoxic, selective recyclable catalytic reagents. Formation of C-N, C-O, C-S, C-F C-C bonds can be seamlessly accomplished by hypervalent catalysed oxidative functionalisations. The aim this review is highlight recent developments the utilisation iodine(III) iodine(V) a wide range including chiral for stereoselective synthesis. Polymer-, magnetic nanoparticle- framework-supported also described.

Language: Английский

Citations

99
Modern approaches towards the synthesis of geminal difluoroalkyl groups DOI
Dayanne R. Carvalho, Alec H. Christian

Organic & Biomolecular Chemistry, Journal Year: 2021, Volume and Issue: 19(5), P. 947 - 964

Published: Jan. 1, 2021

This review will cover the importance of and most recent approaches toward geminal difluoroalkyl groups using transition metal-mediated, photochemical, organocatalytic, other methods.

Language: Английский

Citations

65
Chemoselective Hydro(Chloro)pentafluorosulfanylation of Diazo Compounds with Pentafluorosulfanyl Chloride DOI

Jia‐Yi Shou,

Xiu‐Hua Xu, Feng‐Ling Qing

et al.

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(28), P. 15271 - 15275

Published: April 30, 2021

Abstract Pentafluorosulfanyl chloride (SF 5 Cl) is the most prevalent reagent for incorporation of SF group into organic compounds. However, preparation Cl often relies on hazardous reagents and specialized apparatus. Herein, we described a safe practical synthesis bench‐stable easy‐to‐handle solution in n ‐hexane under gas‐reagent‐free conditions. The synthetic application was demonstrated through unprecedented reaction with diazo chemoselective hydro‐ chloropentafluorosulfanylations α‐diazo carbonyl compounds were developed presence K 3 PO 4 or copper catalyst, respectively. These reactions provide direct efficient access to various α‐pentafluorosulfanyl high value potential applications.

Language: Английский

Citations

60
Expanding organofluorine chemical space: the design of chiral fluorinated isosteres enabled by I(i)/I(iii) catalysis DOI Creative Commons

Stephanie Meyer,

Joel Häfliger, Ryan Gilmour

et al.

Chemical Science, Journal Year: 2021, Volume and Issue: 12(32), P. 10686 - 10695

Published: Jan. 1, 2021

Short aliphatic groups are prevalent in bioactive small molecules and play an essential role regulating physicochemistry molecular recognition phenomena.

Language: Английский

Citations

56
Regio‐ and Enantioselective Intermolecular Aminofluorination of Alkenes via Iodine(I)/Iodine(III) Catalysis** DOI

Michael Schäfer,

Timo Stünkel,

Constantin G. Daniliuc

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(32)

Published: May 18, 2022

The regio- and enantio-selective, intermolecular vicinal fluoroamination of α-trifluoromethyl styrenes has been achieved by enantioselective I

Language: Английский

Citations

42
Regioselective, catalytic 1,1-difluorination of enynes DOI Creative Commons
Zixuan Wang, Keith Livingstone,

Carla Hümpel

et al.

Nature Chemistry, Journal Year: 2023, Volume and Issue: 15(11), P. 1515 - 1522

Published: Oct. 16, 2023

Fluorinated small molecules are prevalent across the functional small-molecule spectrum, but scarcity of naturally occurring sources creates an opportunity for creative endeavour in developing routes to access these important materials. Iodine(I)/iodine(III) catalysis has proven be particularly well-suited this task, enabling abundant alkene substrates readily intercepted by situ-generated λ3-iodanes and processed high-value (di)fluorinated products. These organocatalysis paradigms often emulate metal-based processes engaging π bond and, case styrenes, facilitating fluorinative phenonium-ion rearrangements generate difluoromethylene units. Here we demonstrate that enynes competent proxies thereby mitigating recurrent need aryl substituents, highly versatile homopropargylic difluorides generated operationally simple manner. The scope method is disclosed, together with application target synthesis (>30 examples, up >90% yield).

Language: Английский

Citations

27
Enantioselective Construction of Tertiary Fluoride Stereocenters by Organocatalytic Fluorocyclization DOI Creative Commons
Qiang Wang, Marvin Lübcke, Maria Biosca

et al.

Journal of the American Chemical Society, Journal Year: 2020, Volume and Issue: 142(47), P. 20048 - 20057

Published: Nov. 16, 2020

1,1-Disubstituted styrenes with internal oxygen and nitrogen nucleophiles undergo oxidative fluorocyclization reactions in situ generated chiral iodine(III)-catalysts. The resulting fluorinated tetrahydrofurans pyrrolidines contain a tertiary carbon–fluorine stereocenter. Application of new 1-naphthyllactic acid-based iodine(III)-catalyst allows the control stereocenters up to 96% ee. Density functional theory calculations are performed investigate details mechanism factors governing stereoselectivity reaction.

Language: Английский

Citations

66
Catalytic asymmetric nucleophilic fluorination using BF3·Et2O as fluorine source and activating reagent DOI Creative Commons
Weiwei Zhu, Xiang Zhen, Jingyuan Wu

et al.

Nature Communications, Journal Year: 2021, Volume and Issue: 12(1)

Published: June 25, 2021

Fluorination using chiral catalytic methods could result in a direct access to asymmetric fluorine chemistry. However, challenges fluorinations, especially the longstanding stereochemical existed BF3·Et2O-based have not yet been addressed. Here we report nucleophilic fluorination BF3·Et2O as reagent presence of iodine catalyst. Various fluorinated oxazine products were obtained with good excellent enantioselectivities (up >99% ee) and diastereoselectivities >20:1 dr). Control experiments (the desired fluoro-oxazines be when Py·HF or Et3N·3HF employed source) indicated that acted only but also activating for activation iodosylbenzene.

Language: Английский

Citations

48
Organoiodine-Catalyzed Enantioselective Intermolecular Oxyamination of Alkenes DOI

Chisato Wata,

Takuya Hashimoto

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(4), P. 1745 - 1751

Published: Jan. 22, 2021

Metal-free, catalytic enantioselective intermolecular oxyamination of alkenes is realized by use organoiodine(I/III) chemistry. The protocol applicable toward aryl- and alkyl-substituted with high enantioselectivity electronically controlled regioselectivity. oxyaminated products can be easily deprotected in one step to reveal free amino alcohols yields without loss enantioselectivity. A key our success the discovery a virtually unexplored chemical entity, N-(fluorosulfonyl)carbamate, as bifunctional N,O-nucleophile.

Language: Английский

Citations

47