RSC主编推荐：有机领域精彩文章快览（免费阅读原文）

英国皇家化学会（RSC）是一个超过175年历史的面向全球化学家的非营利会员制机构，旗下拥有44种期刊，其中很多在化学领域有很高影响力。为了进一步帮助广大读者追踪科技前沿热点，X-MOL团队与英国皇家化学会合作，推出英国皇家化学会期刊主编推荐的精彩文章快览，本期文章属“有机领域”，英文点评来自英国皇家化学会期刊的主编。如果大家对我们的解读有更多的补充和点评，欢迎在文末写评论发表您的高见！

Chemical Science (IF: 9.063)

1. Silver-mediated oxidative functionalization of alkylsilanes

Chem. Sci., 2018, Advance Article

DOI: 10.1039/C8SC03730B

Researchers in China have prepared a general approach for the functionalisation of aliphatic C-Si bonds in the presence of silver salts and oxidants. This includes the conversion of C–Si bond to  C–OCF₃, C–OBz, C–OCOCF₃, C–SCF₃, C–SCN, and C–N₃  bonds. The authors demonstrate the first example of trifluoromethoxylation of alkylsilanes.

南开大学的研究人员们发展了一种在银盐和氧化剂存在下脂肪族C-Si键官能化的通用方法。该方法包括将C-Si键转化为C–OCF₃、C–OBz、C–OCOCF₃、C–SCF₃、C–SCN和C–N₃键。作者们还展示了首个烷基硅烷三氟甲氧基化的实例。

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2. A general electrochemical strategy for the Sandmeyer reaction

Chem. Sci., 2018, Advance Article

DOI: 10.1039/C8SC03346C

Researchers in China have demonstrated a general electrochemical strategy for the Sandmeyer halogenation of aryl diazonium salts, which uses simple and inexpensive halogen sources. They can perform these electrochemical reactions using anilines as the starting material in a one-pot fashion.

北京大学的研究人员展示了通过电化学方法可以实现芳基重氮盐的桑德迈尔（Sandmeyer）卤化反应，该过程使用简单且廉价的卤素源，可使用苯胺作为起始材料以一锅法实现。

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Organic Chemistry Frontiers (IF: 5.455)

1. Enantioselective isoquinuclidine synthesis via sequential Diels–Alder/visible-light photoredox C–C bond cleavage: a formal synthesis of the indole alkaloid catharanthine

Org. Chem. Front., 2018, 5, 2934-2939

DOI: 10.1039/C8QO00849C

An enantioselective route to substituted chiral isoquinuclidines, present in alkaloids such as catharanthine, deserpidine, ibogamine and ibogaine, has been developed using a “ketene equivalent” approach. Organocatalyzed Diels–Alder reaction of an N-protected dihydropyridine with acrolein using a valine derived 1,2-aminoalcohol catalyst occurs with high er and dr. Subsequent Ru(Bipy)₃Cl₂•(H₂O)₆catalyzed photoredox cleavage generates an N-protected isoquinuclidinone, providing rapid access to the core structures of a variety of important indole alkaloids. The two-step sequence utilizes acrolein as a ketene dienophile equivalent providing a new approach to asymmetric “ketene” Diels–Alder reactions. Further elaboration of the resultant isoquinuclidines permitted an enantioselective route to intermediates previously employed in total syntheses of catharanthine and deserpidine.

多伦多大学的研究人员使用“烯酮等价物”的方法发展了一种对映选择性的方法合成取代的手性异奎宁环，该结构存在于长春质碱、地舍平、伊菠胺和伊博格碱等生物碱中。他们使用缬氨酸衍生的1,2-氨基醇作为催化剂，N-保护的二氢吡啶与丙烯醛发生有机分子催化的Diels-Alder反应，具有很高的er和dr值，随后发生Ru(Bipy)₃Cl₂•(H₂O)₆ 催化的光氧化还原裂解反应，生成N-保护的异奎宁环酮，能够快速构建各种重要吲哚生物碱的核心结构。这种两步依序合成方法利用丙烯醛作为烯酮亲双烯体等价物，为不对称“烯酮”Diels-Alder反应提供了新方法。对所合成的异奎宁环进一步处理可以对映选择性地合成中间体，这种中间体之前一直用于长春质碱和地舍平的全合成。

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2. Dual roles of ynoates: desymmetrization of dicarboxylic acids using trialkylamines as alkyl equivalents

Org. Chem. Front., 2018, 5, 2955-2959

DOI: 10.1039/C8QO00919H

A novel method has been developed for the desymmetrization of aromatic dicarboxylic acids by employing an esterification reaction/conjugate addition of a carboxyl group to ynoates, which can trigger a coupling reaction. This one-pot cascade transformation, utilizing trialkylamines as alkyl sources for esterification, and ethyl propiolate as a protective or coupling reagent for carboxyl functions (hydrolysis, amidation, esterification, and thioesterification), leads to an asymmetric dicarbonyl target skeleton in a selective manner.

上海工程技术大学的研究人员发展了一种芳香族二羧酸去对称化的新方法，通过酯化/羰基对炔酯的共轭加成反应，继而引发偶联过程。这种一锅法的串联转化利用三烷基胺作为酯化的烷基源，丙炔酸乙酯作为羧基官能团（水解、酰胺化、酯化和硫酯化）的保护试剂或偶联试剂，选择性地构建不对称的二羰基目标骨架。

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