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Photo- and Metal-Mediated Deconstructive Approaches to Cyclic Aliphatic Amine Diversification
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2023-05-12 , DOI: 10.1021/jacs.3c01318 David M Soro 1 , Jose B Roque 1 , Jonas W Rackl 1 , Bohyun Park 2, 3 , Stefan Payer 1 , Yuan Shi 4 , J Craig Ruble 4 , Alexey L Kaledin 5 , Mu-Hyun Baik 2, 3 , Djamaladdin G Musaev 5 , Richmond Sarpong 1
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2023-05-12 , DOI: 10.1021/jacs.3c01318 David M Soro 1 , Jose B Roque 1 , Jonas W Rackl 1 , Bohyun Park 2, 3 , Stefan Payer 1 , Yuan Shi 4 , J Craig Ruble 4 , Alexey L Kaledin 5 , Mu-Hyun Baik 2, 3 , Djamaladdin G Musaev 5 , Richmond Sarpong 1
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Described herein are studies toward the core modification of cyclic aliphatic amines using either a riboflavin/photo-irradiation approach or Cu(I) and Ag(I) to mediate the process. Structural remodeling of cyclic amines is explored through oxidative C–N and C–C bond cleavage using peroxydisulfate (persulfate) as an oxidant. Ring-opening reactions to access linear aldehydes or carboxylic acids with flavin-derived photocatalysis or Cu salts, respectively, are demonstrated. A complementary ring-opening process mediated by Ag(I) facilitates decarboxylative Csp3–Csp2 coupling in Minisci-type reactions through a key alkyl radical intermediate. Heterocycle interconversion is demonstrated through the transformation of N-acyl cyclic amines to oxazines using Cu(II) oxidation of the alkyl radical. These transformations are investigated by computation to inform the proposed mechanistic pathways. Computational studies indicate that persulfate mediates oxidation of cyclic amines with concomitant reduction of riboflavin. Persulfate is subsequently reduced by formal hydride transfer from the reduced riboflavin catalyst. Oxidation of the cyclic aliphatic amines with a Cu(I) salt is proposed to be initiated by homolysis of the peroxy bond of persulfate followed by α-HAT from the cyclic amine and radical recombination to form an α-sulfate adduct, which is hydrolyzed to the hemiaminal. Investigation of the pathway to form oxazines indicates a kinetic preference for cyclization over more typical elimination pathways to form olefins through Cu(II) oxidation of alkyl radicals.
中文翻译：
光介导和金属介导的环脂肪胺多样化解构方法
本文描述的是使用核黄素/光辐照方法或 Cu(I) 和 Ag(I) 来调解该过程，对环状脂肪胺进行核心修饰的研究。使用过二硫酸盐（过硫酸盐）作为氧化剂，通过氧化性 C-N 和 C-C 键裂解探索环胺的结构重塑。证明了分别通过黄素衍生的光催化或铜盐的开环反应获得直链醛或羧酸。由 Ag(I) 介导的互补开环过程促进脱羧 Csp 3 –Csp 2通过关键的烷基自由基中间体在 Minisci 型反应中偶联。通过使用烷基自由基的 Cu(II) 氧化将 N-酰基环胺转化为恶嗪，证明了杂环相互转化。这些转换通过计算进行研究，以告知所提出的机械途径。计算研究表明，过硫酸盐介导环胺的氧化，同时伴随核黄素的减少。过硫酸盐随后通过从还原的核黄素催化剂转移的甲醛氢化物而被还原。环状脂肪胺与 Cu(I) 盐的氧化被认为是由过硫酸盐的过氧键均裂引发的，随后来自环状胺的 α-HAT 和自由基重组形成 α-硫酸盐加合物，其水解为半缩醛胺。
更新日期：2023-05-12
中文翻译：
光介导和金属介导的环脂肪胺多样化解构方法
本文描述的是使用核黄素/光辐照方法或 Cu(I) 和 Ag(I) 来调解该过程，对环状脂肪胺进行核心修饰的研究。使用过二硫酸盐（过硫酸盐）作为氧化剂，通过氧化性 C-N 和 C-C 键裂解探索环胺的结构重塑。证明了分别通过黄素衍生的光催化或铜盐的开环反应获得直链醛或羧酸。由 Ag(I) 介导的互补开环过程促进脱羧 Csp 3 –Csp 2通过关键的烷基自由基中间体在 Minisci 型反应中偶联。通过使用烷基自由基的 Cu(II) 氧化将 N-酰基环胺转化为恶嗪，证明了杂环相互转化。这些转换通过计算进行研究，以告知所提出的机械途径。计算研究表明，过硫酸盐介导环胺的氧化，同时伴随核黄素的减少。过硫酸盐随后通过从还原的核黄素催化剂转移的甲醛氢化物而被还原。环状脂肪胺与 Cu(I) 盐的氧化被认为是由过硫酸盐的过氧键均裂引发的，随后来自环状胺的 α-HAT 和自由基重组形成 α-硫酸盐加合物，其水解为半缩醛胺。
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