ChemRxiv | 2021年诺贝尔化学奖得主的科学探索

以下文章来源于ACS美国化学会 ，作者ACS Publications

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2021年诺贝尔化学奖颁给了来自德国马克斯-普朗克研究所的 Benjamin List 和来自美国普林斯顿大学的 David W. C. MacMillan，以表彰他们在开发不对称有机催化方面的工作。不对称有机催化已被证明是构建分子的强大工具，同时为药物研究开辟了新的途径。

自2017年底 ChemRxiv 预印本平台推出后，Benjamin List 和 David W. C. MacMillan 先后在 ChemRxiv 上发布了他们重要的研究工作，实践着新的科学探索。下面是这些预印本的简要信息，扫描文章二维码即可免费获取全文。欢迎大家关注阅读！

Unified Synthesis of Polycyclic Alkaloids via Complementary Carbonyl Activation

Guoli He, Benjamin List* and Mathias Christmann*

DOI: 10.26434/chemrxiv.14054558.v1

Abstract

A complementary dual carbonyl activation strategy for the synthesis of polycyclic alkaloids has been developed. Successful applications include the synthesis of tetracyclic alkaloids harmalanine, harmalacinine, pentacyclic indoloquinolizidine alkaloid nortetoyobyrine, and octacyclic β-carboline alkaloid peganumine A. The latter synthesis features a protecting-group-free assembly and an asymmetric disulfonimide catalyzed cyclization. Furthermore, formal syntheses of hirsutine, deplancheine, 10-desbromoarborescidine A, and oxindole alkaloids rhynchophylline and isorhynchophylline have been achieved. Finally, a concise synthesis of berberine alkaloid ilicifoline B was completed.

Version History: Feb 19, 2021 Version 1

Decarboxylative sp3 C–N Coupling via Dual Copper/Photoredox Catalysis

Yufan Liang, Xiaheng Zhang and David W. C. MacMillan*

DOI: 10.26434/chemrxiv.5877868.v1

Abstract

Over the last three decades, significant progress has been made in the development of methods to construct sp2 C–N bonds using palladium, copper, or nickel catalysis. However, the incorporation of alkyl substrates to form sp3 C–N bonds remains one of the major challenges in the field of cross-coupling chemistry. Here, we demonstrate that the synergistic combination of copper catalysis and photoredox catalysis can provide a general platform to address this long-standing challenge. This novel cross-coupling system employs naturally abundant alkyl carboxylic acids and commercially available N-nucleophiles as coupling partners, and is applicable to a wide variety of primary, secondary, and tertiary alkyl carboxylic acids (via in situ iodonium activation). At the same time, a vast array of N-nucleophiles, including N-heterocycles, amides, sulfonamides, and anilines, can undergo C–N coupling to provide N-alkyl products in good to excellent efficiency at room temperature and in short order (5 minutes to 1 hour). We have also demonstrated that this C–N coupling protocol can be applied to substrates bearing multiple amines with high regioselectivity, as well as complex drug molecules, enabling the rapid construction of molecular complexity and the late stage functionalization of bioactive pharmaceuticals.

Version History: Feb 12, 2018 Version 1

(the related journal article was published in Nature on Jun 20, 2018, doi: 10.1038/s41586-018-0234-8)

Kinetic Study of Disulfonimide Catalyzed Cyanosilylation of Aldehyde Using a Method of Progress Rates

Zhipeng Zhang*, Martin Klussmann and Benjamin List

DOI: 10.26434/chemrxiv.12084768.v1

Abstract

Kinetic study of organic reactions, especially multistep catalytic reactions, is crucial to in-depth understanding of reaction mechanisms. Here we report our kinetic study of the chiral disulfonimide catalyzed cyanosilylation of aldehyde, which reveals that two molecules of TMSCN are involved in the rate-determining C-C bond forming step. In addition, the apparent activation energy, enthalpy of activation and entropy of activation were deduced through the study of temperature dependence of the reaction rates. More importantly, a novel and efficient method which makes use of the progress rates was developed to treat the kinetic data obtained from continuous monitoring of the reaction progress with in situ FT-IR.

Version History: Apr 06, 2020 Version 1

(the related journal article was published in Synlett on Sep 16, 2020, doi: 10.1055/s-0040-1707129)

An Expedited Phenotypic Approach Towards Organic Reaction Generality

Cesar N. Prieto Kullmer*, Jacob A. Kautzky*, Shane W. Krska, Timothy Nowak, Spencer D. Dreher and David W. C. MacMillan

DOI: 10.33774/chemrxiv-2021-8f5ws

Abstract

Reaction generality is crucial in determining the overall impact and usefulness of organic synthetic methods. In contrast, contemporary generalization processes seem unable to meet the growing demand for robust methodology. We sought to develop an accelerated approach towards achieving generality, inspired by phenotypic screening, that rapidly expands the scope and utility of synthetic methods. This approach was validated by example of the metallaphotoredox decarboxylative arylation, resulting in the discovery of a novel additive that overcomes many lingering limitations of this method and has significant mechanistic implications for nickel-catalyzed cross couplings in general.

Version History: Oct 15, 2021 Version 1

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原标题：《ChemRxiv | 2021年诺贝尔化学奖得主的科学探索》

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