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Enantioselective α-Boryl Carbene Transformations 对映选择性 α-羰基转化

IF 2 4区化学 Q3 CHEMISTRY, ORGANIC

Synlett

Pub Date : 2024-06-04 DOI: 10.1055/a-2338-4544

Shou-Fei Zhu, Ming-Yao Huang

α-Boryl carbenes, which are hybrid structures combining elements of carbenes and boryl groups, represent promising intermediates for constructing organoboron compounds. However, these carbenes are challenging to synthesize and exhibit limited structural diversity. Moreover, their applications in asymmetric transformations remain largely unexplored. In this study, we utilized boryl cyclopropenes as precursors to rapidly synthesize α-Bpin metal carbenes, a novel category of intermediates critical for the synthesis of chiral organoboron molecules. Facilitated by a copper complex modified by a chiral bisoxazoline ligand, these α-boryl carbenes participate in a range of highly enantioselective transfer reactions, including B–H and Si–H insertions, as well as cyclopropanation and cyclopropanation/Cope rearrangement processes. This methodology provides access to previously inaccessible, yet highly useful, chiral organoborons, thereby significantly advancing both carbene and organoboron chemistry.

α-硼烯烃是结合了烯烃和硼烷基元素的混合结构，是构建有机硼化合物的有前途的中间体。然而，这些碳烯化合物的合成具有挑战性，而且结构多样性有限。此外，它们在不对称转化中的应用在很大程度上仍未得到探索。在这项研究中，我们利用硼烷基环丙烯作为前体，快速合成了α-Bpin 金属碳烯，这是一类对合成手性有机硼分子至关重要的新型中间体。在手性双噁唑啉配体修饰的铜络合物的促进下，这些α-硼烷基碳烯参与了一系列高度对映选择性的转移反应，包括 B-H 和 Si-H 插入，以及环丙烷化和环丙烷化/科普重排过程。这种方法提供了获得以前无法获得但非常有用的手性有机硼的途径，从而极大地推动了碳烯和有机硼化学的发展。

引用次数: 0

His-Tagging: Exploring Precise Chemical Modification of Histidine-Containing Bioactive Peptide Sequences His-Tagging：探索对含组氨酸生物活性肽序列的精确化学修饰

IF 2 4区化学 Q2 Chemistry

Synlett

Pub Date : 2024-06-03 DOI: 10.1055/s-0043-1775364

Sourav Chatterjee, Bishwajit Paul, Govindaswamy Shanker

The modification of biomolecules, particularly peptides, has garnered considerable attention from researchers, effectively serving as a connection between chemistry and biology. The modification of peptides can facilitate, among others, the generation of peptide drugs, antibody–drug conjugates, and probes for molecular imaging. Herein, we have carefully curated reactions and chemical transformations of bioactive peptide sequences equipped with histidine amino acids that are conducive for biological applications. This Account also highlights strategies for the chemical modification of histidine that might capture the imagination of both peptide researchers and synthetic chemists.

1 Introduction

2 Histidine Modification in Bioactive Peptides and Proteins

3 Remote Bioactive Peptides and Protein Modification Adjacent to Histidine

4 Conclusions and Future Directions

生物大分子（尤其是肽类）的修饰已引起研究人员的极大关注，它实际上是化学与生物学之间的纽带。肽的修饰可以促进肽药物、抗体药物共轭物和分子成像探针等的生成。在此，我们精心整理了含有组氨酸的生物活性肽序列的反应和化学转化，这些反应和化学转化有利于生物应用。本报告还重点介绍了组氨酸化学修饰的策略，这些策略可能会激发多肽研究人员和合成化学家的想象力。1 引言 2 生物活性肽和蛋白质中的组氨酸修饰 3 组氨酸邻位的远程生物活性肽和蛋白质修饰 4 结论和未来方向

引用次数: 0

Cyclization by metal-catalyzed hydrogen atom transfer/radical-polar crossover 通过金属催化的氢原子转移/自由基-极性交叉实现环化

IF 2 4区化学 Q3 CHEMISTRY, ORGANIC

Synlett

Pub Date : 2024-06-03 DOI: 10.1055/a-2337-2498

Hiroki Shigehisa

Catalytic transformation of alkenes via the metal-hydride hydrogen atom transfer (MHAT) mechanism has notably advanced synthetic organic chemistry. This review focuses on MHAT/radical-polar crossover (MHAT/RPC) conditions, offering a novel perspective on generating electrophilic intermediates and facilitating various intramolecular reactions. Upon using cobalt hydrides, the MHAT mechanism displayed exceptional chemoselectivity and functional group tolerance, making it invaluable for the construction of complex biologically relevant molecules under mild conditions. Recent developments have enhanced regioselectivity and expanded the scope of MHAT-type reactions, enabling the formation of cyclic molecules via hydroalkoxylation, hydroacyloxylation, and hydroamination. Notably, the addition of an oxidant to traditional MHAT systems enables the synthesis of rare cationic alkylcobalt(IV) complexes, bridging radical mechanisms to ionic reaction systems. This review culminates with examples of natural product syntheses and exploration of asymmetric intramolecular hydroalkoxylation, highlighting the ongoing challenges and opportunities for future research to achieve higher enantioselectivity. This comprehensive study revisits the historical evolution of the MHAT mechanism and provides the groundwork for further innovations in the synthesis of structurally diverse and complex natural products.1 Introduction2 Intramolecular hydroalkoxylation and hydroacyloxylation reactions3 Intramolecular hydroamination reactions4 Intramolecular hydroarylation reactions5 Deprotective cyclization6 Asymmetric intramolecular hydroalkoxylation

通过金属氢化物氢原子转移（MHAT）机制对烯进行催化转化，显著推动了合成有机化学的发展。本综述侧重于 MHAT/自由基-极性交叉（MHAT/RPC）条件，为生成亲电中间体和促进各种分子内反应提供了新的视角。在使用钴氢化物时，MHAT 机制显示出卓越的化学选择性和官能团耐受性，使其成为在温和条件下构建复杂生物相关分子的宝贵手段。最近的研究进展提高了 MHAT 类反应的区域选择性并扩大了其范围，使其能够通过氢烷氧基化、氢异烷氧基化和氢氨基化形成环状分子。值得注意的是，在传统的 MHAT 系统中加入氧化剂可合成罕见的阳离子烷基钴（IV）复合物，从而将自由基机制与离子反应系统连接起来。本综述以天然产物合成和分子内不对称氢烷氧基化的探索为例，强调了未来研究在实现更高的对映选择性方面所面临的挑战和机遇。本综合研究回顾了 MHAT 机理的历史演变，为进一步创新合成结构多样、复杂的天然产物奠定了基础。

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引用次数: 0

Aliphatic Olefin Epoxidation with Hydrogen Peroxide Catalyzed by an Integrated Mn/TS-1/N System Mn/TS-1/N 集成系统催化的脂肪族烯烃与过氧化氢的环氧化反应

IF 2 4区化学 Q2 Chemistry

Synlett

Pub Date : 2024-05-28 DOI: 10.1055/s-0043-1775366

Shanxiu Yang, Yuyu Liu, Zhang Zhang, Bo Qian

Propylene liquid-phase epoxidation with 50–75% H₂O₂ is an important process for the industrial production of propylene oxide (PO). To realize a propylene epoxidation process that proceeds with low hydrogen peroxide concentration, we developed an integrated Mn/TS-1/N catalytic system via in-situ reaction of Mn/TS-1 with an N-donor ligand, affording the PO product in excellent yield with only 30 wt% H₂O₂. Other long-chain aliphatic epoxides were also readily synthesized by this catalytic epoxidation system. Moreover, in addition to the standard micro-pressure reactor, a continuous-flow microreactor was developed that executed the hydrogen peroxide propylene oxide (HPPO) process with excellent efficiency for 1300 hours. This innovative Mn/TS-1/N catalyzed epoxidation represents a promising direction for advancing HPPO industrial processes, offering improved efficiency while minimizing the reliance on high concentrations of H₂O₂.

丙烯液相环氧化（50-75% H2O2）是环氧丙烷（PO）工业生产的重要工艺。为了实现低过氧化氢浓度下的丙烯环氧化工艺，我们开发了一种集成的 Mn/TS-1/N 催化系统，通过 Mn/TS-1 与 N-供体配体的原位反应，只需 30 wt% 的 H2O2 即可获得产率极高的环氧丙烷产品。其他长链脂肪族环氧化物也很容易通过这种催化环氧化体系合成。此外，除了标准的微压反应器外，还开发了一种连续流微反应器，可在 1300 小时内高效执行过氧化氢环氧丙烷（HPPO）工艺。这种创新的 Mn/TS-1/N 催化环氧化技术代表了推进 HPPO 工业流程的一个有前途的方向，它在提高效率的同时，最大限度地减少了对高浓度 H2O2 的依赖。

引用次数: 0

Copper(II) Triflate Catalyzed Rearrangement of Amino 2,3-Epoxides to α-Amino Ketones 三氟化铜（II）催化 2,3-环氧化氨基酮与α-氨基酮的重排反应

IF 2 4区化学 Q2 Chemistry

Synlett

Pub Date : 2024-05-23 DOI: 10.1055/s-0043-1775367

Sunisa Akkarasamiyo, Saranya Chitsomkhuan, Supawadee Buakaew, Joseph S. M. Samec, Pitak Chuawong, Jenjira Saymaya, Punlop Kuntiyong, Wanchai Pluempanupat

α-Amino ketones were synthesized by a Meinwald rearrangement of biomass-based amino epoxides using copper(II) triflate as a catalyst. The regioselectivity of the rearrangement can be rationalized in terms of the reaction proceeding via the most stable carbocationic intermediate to give various α-amino α′-aryl ketones in moderate to good yields. This is an attractive method to prepare α-amino ketones using a benign and inexpensive catalyst.

以三酸化铜（II）为催化剂，通过生物质基氨基环氧化物的梅因沃尔德重排合成了 α-氨基酮。该重排反应的区域选择性是通过最稳定的碳代中间体进行的，从而以中等至良好的产率得到各种 α-氨基 α′-芳基酮。这是一种使用良性廉价催化剂制备α-氨基酮的极具吸引力的方法。

引用次数: 0

Multicomponent Reactions: A Promising Approach to Isotope Labeling 多组分反应：同位素标记的可行方法

IF 2 4区化学 Q2 Chemistry

Synlett

Pub Date : 2024-05-22 DOI: 10.1055/a-2331-6399

Siyu Xiao, Antonio Conte, Baart Cornelissen, Alexander Dömling, Philip H. Elsinga

Isotopic labeling is an attractive modality that has been widely used in many aspects of chemistry, the life sciences, and medical research; especially deuterated drugs and radioactive molecules have been used in the diagnosis and treatment of cancer and neurodegenerative diseases. The widespread application and rapid development of isotopically -labeled molecules has led to an increased demand for new isotopic labeling chemical methods to synthesize highly specific molecules bearing defined nuclides. Multicomponent reactions (MCRs) are modular build-up approaches for the rapid generation of complex molecules often containing biologically relevant scaffold structures. There is great potential to use MCRs to construct isotopically labeled molecules because assembly speed and reaction diversity are key advantages of MCR. In this review, we provide an overview of the recent literature on this topic that can provide insight into the application of MCRs in the field of isotopic labeling.

同位素标记是一种极具吸引力的方法，已被广泛应用于化学、生命科学和医学研究的许多方面；特别是氘化药物和放射性分子已被用于癌症和神经退行性疾病的诊断和治疗。同位素标记分子的广泛应用和快速发展，导致对新同位素标记化学方法的需求不断增加，以合成含有特定核素的高特异性分子。多组分反应（MCR）是一种快速生成复杂分子的模块化方法，通常包含生物相关的支架结构。由于组装速度和反应多样性是多组分反应的主要优势，因此利用多组分反应构建同位素标记分子具有很大的潜力。在这篇综述中，我们将概述有关这一主题的最新文献，以便深入了解 MCR 在同位素标记领域的应用。

引用次数: 0

Deucravacitinib Induces Proteasomal Degradation of YAP1 in Human Glioblastoma Cells 去氯伐替尼诱导人胶质母细胞瘤细胞中 YAP1 的蛋白酶体降解

IF 2 4区化学 Q2 Chemistry

Synlett

Pub Date : 2024-05-22 DOI: 10.1055/a-2331-6463

Shaonan Wang, Min Sun, Yajuan Su, Zhou Xu, Ang Li, Weiwei He

Deucravacitinib is a selective allosteric inhibitor of tyrosine kinase 2 (TYK2) recently approved by the FDA for the treatment of plaque psoriasis. We discovered that this compound induces proteasomal degradation of YAP1, the downstream effector of the Hippo signaling pathway, in human glioblastoma (GBM) cells (U-87 MG). This degradation is independent of the canonical Hippo pathway, which offers clues to alternative mechanisms for YAP1 regulation.

Deucravacitinib 是酪氨酸激酶 2 (TYK2) 的一种选择性异位抑制剂，最近被美国食品及药物管理局批准用于治疗斑块型银屑病。我们发现，这种化合物能诱导人胶质母细胞瘤（GBM）细胞（U-87 MG）中希波信号通路下游效应因子 YAP1 蛋白质体降解。这种降解独立于典型的 Hippo 通路，为 YAP1 的替代调控机制提供了线索。

引用次数: 0

Copper−Promoted Dimerization of Benzyl Thiocyanates to Access Functionalized Bibenzyls 铜促进硫氰酸苄酯二聚化以获得官能化的比本苄

IF 2 4区化学 Q2 Chemistry

Synlett

Pub Date : 2024-05-21 DOI: 10.1055/a-2330-9955

Sandeep Singh, S. R. De

The synthesis of bibenzyl derivatives holds significance in organic chemistry due to their diverse pharmacological and synthetic applications. Herein, we report a novel copper–promoted dimerization reaction for the efficient synthesis of functionalized bibenzyls from benzyl thiocyanates. The coupling reaction proceeds under aerobic and mild conditions via cascade C–S bond cleavage in one pot. Diverse substituents including electron–withdrawing groups on the aryl ring are well–tolerated to afford the desired products in moderate to good yields. The developed protocol could be utilized to obtain the cross coupling product from two different electron–deficient benzyl thiocyanates.

由于联苄衍生物具有多种药理和合成应用，因此其合成在有机化学中具有重要意义。在此，我们报告了一种新型的铜促进二聚反应，用于从硫氰酸苄酯高效合成功能化的联苄。该偶联反应在有氧和温和的条件下通过级联 C-S 键裂解在一锅中进行。芳基环上的各种取代基（包括抽电子基团）都能很好地耐受，从而以中等至较高的产率得到所需的产物。所开发的方案可用于从两种不同的缺电子硫氰酸苄酯中获得交叉偶联产物。

引用次数: 0

Synthesis of Substituted Cyclooctenes through Cross-Coupling Reactions 通过交叉偶联反应合成取代的环辛烯

IF 2 4区化学 Q2 Chemistry

Synlett

Pub Date : 2024-05-18 DOI: 10.1055/a-2330-0819

Ryuichi Murata, Rakuto Yoshida, Daisuke Uraguchi, Keisuke Asano

Cross-coupling methods for the introduction of various substituents into the olefin moiety of cyclooctenes were developed. A range of 1-substituted cis-cyclooctenes were synthesized. These protocols unlocked routes to previously inaccessible derivatives, allowing for the syntheses of cis-cyclooctenes bearing various functional groups. Moreover, the method was applied to the synthesis of a 1,2-disubstituted trans-cyclooctene for the first time, which proved to be a significantly active organocatalyst in relation to the previously developed monosubstituted trans-cyclooctene.

开发了在环辛烯的烯烃分子中引入各种取代基的交叉偶联方法。合成了一系列 1-取代的顺式环辛烯。这些方法开辟了以前无法获得的衍生物的途径，从而可以合成带有各种官能团的顺式环辛烯。此外，该方法还首次应用于合成 1,2-二取代的反式环辛烯，与之前开发的单取代反式环辛烯相比，它被证明是一种活性显著的有机催化剂。

引用次数: 0

Synthesis of Dihydrobenzosiloles and Silacyclopentane via Double Hydroalumination of Terminal Alkynes 通过末端炔烃的双氢化氨合成二氢苯甲硅烷和硅杂环戊烷

IF 2 4区化学 Q2 Chemistry

Synlett

Pub Date : 2024-05-18 DOI: 10.1055/a-2330-0874

Ryusei Osawa, Kotaro Ogihara, Fumine Hamasaki, H. Kinoshita, Katsukiyo Miura

We developed an efficient method for the synthesis of dihydrobenzosiloles in 19% to 90% isolated yields from 1-hydrosilyl-2-ethynylbenzenes using two equivalents of diisobutylaluminum hydride. The reaction mechanism involves regioselective double hydroalumination of the alkyne moiety followed by cyclization to 2-alanyldihydrobenzosilole. A silacyclopentane was also synthesized in 97% isolated yield from the corresponding 4-silylbut-1-yne under the same reaction conditions. Although the substrate scope was conducted on a 0.5 mmol scale, a gram-scale reaction of 1-diphenylsilyl-2-ethynylbenzene under the optimized reaction conditions successfully afforded the desired product in 94% isolated yield without loss of reactivity.

我们开发了一种高效的方法，利用两个当量的二异丁基氢化铝，从 1- 氢硅烷基-2-乙炔基苯合成二氢苯甲硅烷基，分离产率为 19% 至 90%。反应机理包括炔基的区域选择性双氢化，然后环化成 2-丙烯基二氢苯甲硅醚。在相同的反应条件下，还从相应的 4-硅基丁基-1-炔合成出了一种硅基环戊烷，分离收率为 97%。虽然底物范围是在 0.5 毫摩尔的规模下进行的，但在优化的反应条件下，1-二苯基硅基-2-乙炔基苯的克级反应成功地得到了所需的产物，分离收率为 94%，且没有失去反应活性。

引用次数: 0

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