RSC主編推薦：有機領域精彩文章快覽

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英國皇家化學會（RSC）是一個擁有175年歷史的面向全球化學家的非營利會員制機構，旗下擁有43種期刊，其中很多在化學領域有很高影響力。為了進一步幫助廣大讀者追蹤科技前沿熱點，X-MOL團隊與英國皇家化學會合作，推出英國皇家化學會期刊主編推薦的精彩文章快覽，本期文章屬「有機領域」，英文點評來自英國皇家化學會期刊的主編。如果大家對我們的解讀有更多的補充和點評，歡迎在文末寫評論發表您的高見！

Organic Chemistry Frontiers

(IF: 4.955)

1. A benzothiadiazole-based fluorescent sensor for selective detection of oxalyl chloride and phosgene

Org. Chem. Front., 2017, Advance Article

DOI: 10.1039/C7QO00378A

Oxalyl chloride and phosgene are highly toxic chemicals but are widely used in industrial processes, which have been regarded as a serious threat to our health and public security. Thus, it is imperative to develop a convenient and reliable detection method for these noxious agents. It was reported in this research the rational design of a fluorescent sensor (denoted as BTA) for simultaneously detecting oxalyl chloride and phosgene, in whicho-phenylenediamine (OPD) as the reactive recognition site and benzothiadiazole (BTD) as the fluorophore moiety are coupled into one single benzo-fused motif. The probe works in a 「turn-on」 fluorescence mode due to the formation of piperazine-2,3-dione and 2-imidazolidinone rings by intramolecular cyclization reactions between the OPD part with oxalyl chloride and phosgene, respectively, which greatly inhibits the intramolecular charge transfer (ICT) process from two amines to the BTD core in the sensor BTA. The detection limit of oxalyl chloride and phosgene is as low as 3 nM and 20 nM in solutions, respectively. Moreover, the sensor exhibits outstanding selectivity toward oxalyl chloride and phosgene over the nerve-agent mimic diethyl chlorophosphate and various acyl chlorides. Furthermore, a portable test paper with BTA has been facilely fabricated for visual on-site detection of the two toxic chemicals in the gas phase.

劇毒化學品草醯氯和光氣在工業生產中有著廣泛的應用，被看作是人類健康和公共安全的嚴重威脅。因此，對這些有害物質開展方便可靠的檢測方法勢在必行。在本論文中，江蘇師範大學的李秋艷、王曉軍及其合作者報道了一種用於同時檢測草醯氯和光氣的熒光探針分子（表示為BTA）的合理設計方法，其中作為反應識別位點的鄰苯二胺（OPD）和作為熒光基團的苯並噻二唑（BTD）偶聯形成單一的苯並稠合單元。該探針的OPD基團可與草醯氯或光氣分別發生分子內環化反應，生成哌嗪-2,3-二酮或2-咪唑啉酮環，從而極大地抑制了從兩個氨基到BTD核心的分子內電荷轉移（ICT）過程，開啟探針分子的「turn-on」熒光模式。草醯氯和光氣在溶液中的檢測限分別可低至3 nM和20 nM。而且，相比於神經毒劑類似物二乙基磷醯氯以及多種醯氯，該感測器對草醯氯和光氣具有優異的選擇性。此外，帶有BTA的便攜試紙可方便地製得，用於氣相中兩種有毒化學物質的現場檢測。

2. Transition-metal-free dehydrogenation coupling of pyridinium through a self-promoted hydride transfer process

Org. Chem. Front., 2017, Advance Article

DOI: 10.1039/C7QO00389G

A transition-metal-free intramolecular cross dehydrogenation coupling reaction of pyridinium was developed. The C(sp2)–H/C(sp2)–H coupling reaction involved an unprecedented intermolecular hydride transfer process from the 1,2-dihydropyridine intermediate to another molecule of pyridinium and formed 1,4-dihydropyridine. Unlike the well-known dehydrogenation coupling proceeded under oxidative conditions, this was the first example of the coupling reaction through a substrate self-promoted hydride transfer process.

雲南大學的夏成峰教授及其團隊成功開發了一種無過渡金屬參與的吡啶鎓分子內交叉脫氫偶聯反應。C(sp2)-H/C(sp2)-H鍵的偶聯反應涉及從1,2-二氫吡啶中間體到另一吡啶鎓分子分子間負氫轉移的罕見過程，生成1,4-二氫吡啶產物。與人們熟知的氧化條件下進行脫氫偶聯的反應有所不同，這是首例通過底物自促進負氫轉移過程進行的偶聯反應。

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