Methanol is gaining popularity as a transfer-hydrogenating agent in catalytic reduction reactions because of its bulk-scale production and inexpensive nature. Current research interests include the utilization of methanol as a safe and sustainable hydrogen source for chemical synthesis and drug development. In particular, the chemoselective reduction of α,β-unsaturated ketones is of great interest because of their prevalence in many natural products. We investigated the potential application of acridine-derived SNS-Ru pincer complexes in methanol activation for chemoselective reduction of chalcones. Our developed catalytic system showed broad substrate tolerance, including substrates containing reducible functional groups. Control experiments and postsynthetic applications are also highlighted.
{"title":"Activating Methanol for Chemoselective Transfer Hydrogenation of Chalcones Using an SNS-Ruthenium Complex","authors":"Kailash Mohar, Hirak Jyoti Phukan, Avijit Mondal, Kaushik Soni, Dipankar Srimani","doi":"10.1055/a-2384-6441","DOIUrl":"https://doi.org/10.1055/a-2384-6441","url":null,"abstract":"<p>Methanol is gaining popularity as a transfer-hydrogenating agent in catalytic reduction reactions because of its bulk-scale production and inexpensive nature. Current research interests include the utilization of methanol as a safe and sustainable hydrogen source for chemical synthesis and drug development. In particular, the chemoselective reduction of α,β-unsaturated ketones is of great interest because of their prevalence in many natural products. We investigated the potential application of acridine-derived SNS-Ru pincer complexes in methanol activation for chemoselective reduction of chalcones. Our developed catalytic system showed broad substrate tolerance, including substrates containing reducible functional groups. Control experiments and postsynthetic applications are also highlighted.</p> ","PeriodicalId":22319,"journal":{"name":"Synlett","volume":null,"pages":null},"PeriodicalIF":2.0,"publicationDate":"2024-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142210260","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Hao-Tian Dai, Xu-Lun Huang, Yuan-Zheng Cheng, Shu-Li You
Dearomatization of indole derivatives offers a straightforward approach to accessing the indoline framework. However, highly efficient dearomatization of indoles bearing electron-deficient groups remains underdeveloped. Herein, a nickel-catalyzed intermolecular hydroalkylative dearomatization reaction of indoles with simple alkyl bromides through a single-electron-transfer process is reported. A wide variety of indole derivatives bearing various functional groups were compatible with this protocol and reacted with primary, secondary, or tertiary alkyl bromides to afford a series of indolines in good yields (up to 82%) and with excellent diastereoselectivity (up to >20:1). Notably, a nickel-mediated hydrogen-atom-transfer process was observed when terminal alkyl bromides were employed as the radical precursors, which resulted in branched products.
{"title":"Nickel-Catalyzed Radical Hydroalkylative Dearomatization of Indoles with Alkyl Bromides","authors":"Hao-Tian Dai, Xu-Lun Huang, Yuan-Zheng Cheng, Shu-Li You","doi":"10.1055/a-2382-0292","DOIUrl":"https://doi.org/10.1055/a-2382-0292","url":null,"abstract":"<p>Dearomatization of indole derivatives offers a straightforward approach to accessing the indoline framework. However, highly efficient dearomatization of indoles bearing electron-deficient groups remains underdeveloped. Herein, a nickel-catalyzed intermolecular hydroalkylative dearomatization reaction of indoles with simple alkyl bromides through a single-electron-transfer process is reported. A wide variety of indole derivatives bearing various functional groups were compatible with this protocol and reacted with primary, secondary, or tertiary alkyl bromides to afford a series of indolines in good yields (up to 82%) and with excellent diastereoselectivity (up to >20:1). Notably, a nickel-mediated hydrogen-atom-transfer process was observed when terminal alkyl bromides were employed as the radical precursors, which resulted in branched products.</p> ","PeriodicalId":22319,"journal":{"name":"Synlett","volume":null,"pages":null},"PeriodicalIF":2.0,"publicationDate":"2024-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142210303","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A Fe(OTf)3 and γ-cyclodextrin-catalyzed hydroarylation of alkenes with 1-naphthols or 2-naphthols is demonstrated. This efficient and general method delivers a wide range of benzylic naphthols from readily available starting materials with high chemo- and regioselectivity in up to 99% yield, with no need for a strong base or additive.
{"title":"Iron(III) Triflate and γ-Cyclodextrin-Catalyzed Hydroarylation of Alkenes with 1-Naphthols and 2-Naphthols","authors":"Meng-Xue Hu, Peng Chen, Le-Wei Miao, Jianghuan Shi, Yi-Jun Jiang","doi":"10.1055/a-2382-3010","DOIUrl":"https://doi.org/10.1055/a-2382-3010","url":null,"abstract":"<p>A Fe(OTf)<sub>3</sub> and γ-cyclodextrin-catalyzed hydroarylation of alkenes with 1-naphthols or 2-naphthols is demonstrated. This efficient and general method delivers a wide range of benzylic naphthols from readily available starting materials with high chemo- and regioselectivity in up to 99% yield, with no need for a strong base or additive.</p> ","PeriodicalId":22319,"journal":{"name":"Synlett","volume":null,"pages":null},"PeriodicalIF":2.0,"publicationDate":"2024-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142210302","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
We describe effective development of the highly diastereoselective synthesis of double helical tetraamine 2-H2-C2 and propose a mechanism for its formation. The resolution of 2-H2-C2 is facilitated by a high racemization barrier of 43 kcal mol–1 and it is implemented via either a chiral auxiliary or preparative supercritical fluid chromatography. This enables preparation of the first high-spin neutral diradical, with spin density delocalized within an enantiomeric double helical π-system. The presence of two effective 3-electron C–N bonds in the diradical leads to: (1) the triplet (S = 1) high-spin ground state with a singlet-triplet energy gap of 0.4 kcal mol–1 and (2) the long half-life of up to 6 days in 2-MeTHF at room temperature. The diradical possesses a racemization barrier of at least 26 kcal mol–1 in 2-MeTHF at 293 K and chiroptical properties, with an absorption anisotropy factor |g| ≈ 0.005 at 548 nm. These unique magnetic and optical properties of our diradical form the basis for the development of next-generation spintronic devices.