- Direct photochemical cross-coupling between aliphatic acids and BF3K salts
-
We describe a novel photoredox hetero-coupling reaction of two C (sp3) radicals from aliphatic acids or BF3K salts. The kinetic differences in radical persistence provide cross-selectivity, using an organic photoredox catalyst and an oxidant with visible light. This method exhibits broad scope, including several examples constructing sterically hindered C(sp3)-C(sp3) bonds.
- Sun, Zhuming,Tang, Bingqing,Liu, Kevin K.-C.,Zhu, Hugh Y.
-
-
Read Online
- Highly Robust Iron Catalyst System for Intramolecular C(sp3)?H Amidation Leading to γ-Lactams
-
Disclosed here is the use of an iron catalyst system for an intramolecular C?H amidation toward γ-lactam synthesis from dioxazolone precursors. (Phthalocyanine)FeIIICl was found to catalyze this cyclization with extremely high turnover numbers of up to 47 000 under mild and aerobic conditions. On the basis of experimental and computational mechanistic studies, the reaction is suggested to proceed by a stepwise radical pathway involving fast hydrogen atom abstraction followed by radical rebound. A plausible origin for the high turnover numbers along with air-compatibility is also rationalized.
- Kweon, Jeonguk,Chang, Sukbok
-
supporting information
p. 2909 - 2914
(2020/12/11)
-
- Photocatalytic α-Tertiary Amine Synthesis via C?H Alkylation of Unmasked Primary Amines
-
A practical, catalytic entry to α,α,α-trisubstituted (α-tertiary) primary amines by C?H functionalisation has long been recognised as a critical gap in the synthetic toolbox. We report a simple and scalable solution to this problem that does not require any in situ protection of the amino group and proceeds with 100 percent atom-economy. Our strategy, which uses an organic photocatalyst in combination with azide ion as a hydrogen atom transfer (HAT) catalyst, provides a direct synthesis of α-tertiary amines, or their corresponding γ-lactams. We anticipate that this methodology will inspire new retrosynthetic disconnections for substituted amine derivatives in organic synthesis, and particularly for challenging α-tertiary primary amines.
- Alder, Catherine M.,Ballantyne, George,Cresswell, Alexander J.,Cunningham, William B.,Edwards, Lee J.,Grayson, Matthew N.,Kinsella, Anna G.,McKay, Blandine S. J.,Mules, Tom,Ryder, Alison S. H.,Turner-Dore, Jacob
-
p. 14986 - 14991
(2020/06/20)
-
- Strategic Approach to the Metamorphosis of γ-Lactones to NH γ-Lactams via Reductive Cleavage and C-H Amidation
-
A new approach has elaborated on the conversion of γ-lactones to the corresponding NH γ-lactams that can serve as γ-lactone bioisosteres. This approach consists of reductive C-O cleavage and an Ir-catalyzed C-H amidation, offering a powerful synthetic tool for accessing a wide range of valuable NH γ-lactam building blocks starting from γ-lactones. The synthetic utility was further demonstrated by the late-stage transformation of complex bioactive molecules and the asymmetric transformation.
- Jung, Hoi-Yun,Chang, Sukbok,Hong, Sungwoo
-
p. 7099 - 7103
(2019/09/07)
-
- Synthesis of 5-Substituted 2-Pyrrolidinones by Coupling of Organozinc Reagents with Cyclic N-Acyliminium Ions
-
A coupling reaction between cyclic N-acyliminium ions with organozinc reagents is described. The cyclic N-acyliminium ions, generated in situ from N-substituted-5-hydroxy-2-pyrrolidinones by treatment with boron trifluoride-diethyl ether complex or titani
- Hidalgo-Mercado, Yazmín I.,Olivo, Horacio F.,Romero-Ortega, Moisés,Santos-Sánchez, Zaira A.,Zaragoza-Galicia, Ivann
-
p. 4650 - 4656
(2019/12/11)
-
- Synthesis, antimycobacterial activity and influence on mycobacterial InhA and PknB of 12-membered cyclodepsipeptides
-
In recent years, several small natural cyclopeptides and cyclodepsipeptides were reported to have antimycobacterial activity. Following this lead, a synthetic pathway was developed for a small series of 12-membered ring compounds with one amide and two ester bonds (cyclotridepsipeptides). Within the series, the ring system proved to be necessary for growth inhibition of Mycobacterium smegmatis and Mycobacterium tuberculosis in the low micromolar range. Open-chain precursors and analogues were inactive. The compounds modulated autophosphorylation of the mycobacterial protein kinase B (PknB). PknB inhibitors were active at μM concentration against mycobacteria while inducers were inactive. PknB regulates the activity of the mycobacterial reductase InhA, the target of isoniazid. The activity of the series against Mycobacterium bovis BCG InhA overexpressing strains was indistinguishable from that of the parental strain suggesting that they do not inhibit InhA. All substances were not cytotoxic (HeLa > 5 μg/ml) and did not show any significant antiproliferative effect (HUVEC > 5 μg/ml; K-562 > 5 μg/ml). Within the scope of this study, the molecular target of this new type of small cyclodepsipeptide was not identified, but the data suggest interaction with PknB or other kinases may partly cause the activity.
- Laqua, Katja,Klemm, Marcel,Richard-Greenblatt, Melissa,Richter, Adrian,Liebe, Linda,Huang, Tingting,Lin, Shuangjun,Guardia, Ana,Pérez-Herran, Esther,Ballell, Lluís,Av-Gay, Yossef,Imming, Peter
-
p. 3166 - 3190
(2018/05/05)
-
- Synthesis of γ-Lactams by Mild, o-Benzoquinone-Induced Oxidation of Pyrrolidines Containing Oxidation-Sensitive Functional Groups
-
The late-stage oxidation of substituted pyrrolidines offers good flexibility for the construction of γ-lactam libraries, and especially in recent years the methods for functionalization of pyrrolidine have been available. We reported a new strategy for oxidation of pyrrolidines to γ-lactams: reaction of pyrrolidine with an o-benzoquinone gives an N,O-acetal by direct oxidation of the α-C-H bond of the pyrrolidine ring, and then the N,O-acetal is further oxidized by the o-benzoquinone to the γ-lactam. Because the first oxidation occurs selectively at the α-C-H of the pyrrolidine ring, oxidation-sensitive functional groups (allyl-, vinyl-, hydroxyl-, and amino groups) on pyrrolidine ring are unaffected. The synthetic utility of this novel method was demonstrated by the facile syntheses of (S)-vigabatrin and two analogues.
- Rong, Hao-Jie,Cheng, Yong-Feng,Liu, Fan-Fan,Ren, Shu-Jian,Qu, Jin
-
p. 532 - 540
(2017/04/26)
-
- Synthesis of Substituted γ- and δ-Lactams via Pd-Catalyzed Alkene Carboamination Reactions
-
The synthesis of substituted γ- and δ-lactams via palladium-catalyzed alkene carboamination reactions between aryl halides and alkenes bearing pendant amides is described. The substrates for these reactions are generated in 1-3 steps from commercially ava
- Boothe, Jordan R.,Shen, Yifan,Wolfe, John P.
-
p. 2777 - 2786
(2017/03/14)
-
- Cyclic amidino agents useful as nitric oxide synthase inhibitors
-
The current invention discloses useful amidino derivative useful as nitric oxide synthase inhibitors.
- -
-
-
- Azepine derivatives useful as nitric oxide synthase inhibitors
-
The current invention discloses azepine derivatives useful as nitric oxide synthase inhibitors.
- -
-
-
- 2-Iminopyrrolidines as potent and selective inhibitors of human inducible nitric oxide synthase
-
A series of substituted 2-iminopyrrolidines has been prepared and shown to be potent and selective inhibitors of the human inducible nitric oxide synthase (hiNOS) isoform versus the human endothelial nitric oxide synthase (heNOS) and the human neuronal ni
- Hagen, Timothy J.,Bergmanis, Arija A.,Kramer, Steven W.,Fok, Kam F.,Schmelzer, Albert E.,Pitzele, Barnett S.,Swenton, Lydia,Jerome, Gina M.,Kornmeier, Christine M.,Moore, William M.,Branson, Linda F.,Connor, Jane R.,Manning, Pamela T.,Currie, Mark G.,Hallinan, E. Ann
-
p. 3675 - 3683
(2007/10/03)
-