- Development of the "diverted Heck" Reaction for the Synthesis of Five-Membered Rings
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The "diverted Heck"reaction has been shown to be a potent method to synthesize cyclopropanes from electron-rich olefins and iodomethyl trifluoroborate. Nevertheless, it is not mechanistically limited to the three-membered rings. The synthesis of five-memb
- Breitwieser, Kevin,Chen, Peter
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- Rapid Assessment of the Reaction-Condition-Based Sensitivity of Chemical Transformations
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A systematic, user-friendly assessment tool that delivers a clear overview of the sensitivity of reactions to key parameters is highly desirable. Herein, the development of such a method is described. The intuitive, standardized presentation of the result
- Pitzer, Lena,Sch?fers, Felix,Glorius, Frank
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- Deaminative Borylation of Aliphatic Amines Enabled by Visible Light Excitation of an Electron Donor–Acceptor Complex
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A deaminative strategy for the borylation of aliphatic primary amines is described. Alkyl radicals derived from the single-electron reduction of redox-active pyridinium salts, which can be isolated or generated in situ, were borylated in a visible light-mediated reaction with bis(catecholato)diboron. No catalyst or further additives were required. The key electron donor–acceptor complex was characterized in detail by both experimental and computational investigations. The synthetic potential of this mild protocol was demonstrated through the late-stage functionalization of natural products and drug molecules.
- Sandfort, Frederik,Strieth-Kalthoff, Felix,Klauck, Felix J. R.,James, Michael J.,Glorius, Frank
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supporting information
p. 17210 - 17214
(2018/11/10)
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- Copper(II)-Catalyzed Asymmetric Photoredox Reactions: Enantioselective Alkylation of Imines Driven by Visible Light
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Asymmetric photoredox catalysis offers exciting opportunities to develop new synthetic approaches to chiral molecules through novel reaction pathways. Employing the first-row transition metal complexes as the chiral photoredox catalysts remains, however, a formidable challenge, although these complexes are economic, environmentally friendly, and often exhibit special reactivities. We report in this Article the development of one class of highly efficient asymmetric/photoredox bifunctional catalysts based on the copper(II) bisoxazoline complexes (CuII-BOX) for the light-induced enantioselective alkylation of imines. The reactions proceed under very mild conditions and without a need for any other photosensitizer. The simple catalytic system and readily tunable chiral ligands enable a significantly high level of enantioselectivity for the formation of chiral amine products bearing a tetrasubstituted carbon stereocenter (36 examples, up to 98% ee). Overall, the CuII-BOX catalysts initiate the radical generation, and also govern the subsequent stereoselective transformations. This strategy utilizing chiral complexes comprised of a first-row transition metal and a flexible chiral ligand as the asymmetric photoredox catalysts provides an effective platform for the development of green asymmetric synthetic methods.
- Li, Yanjun,Zhou, Kexu,Wen, Zhaorui,Cao, Shi,Shen, Xiang,Lei, Meng,Gong, Lei
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supporting information
p. 15850 - 15858
(2018/11/23)
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- Synthesis of ortho-Acylbenzylboronates via Cross-Coupling Reaction of (Dialkoxyboryl)methylzinc Reagents with Haloarenes. A Stable ortho-Quinodimethane Precursor
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The cross-coupling reaction of IZnCH2B(OCMe2)2 with iodoarenes in the presence of PdCl2(PPh3)2 produces the corresponding benzylic boronates in high yields.Among them, the benzylic boronates having an acyl group at the ortho position readily undergo the 1,5-rearrangement to the carbonyl oxygen producing the o-quinodimethane derivatives under thermal or photochemical conditions.The reaction provides benzo-fused cycloalkanes by trapping with dienophiles.cross
- Kanai, Gen,Miyaura, Norio,Suzuki, Akira
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p. 845 - 848
(2007/10/02)
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