Palladium-catalyzed Br/D exchange of arenes: selective deuterium incorporation with versatile functional group tolerance and high efficiency

Zhang, Hong-Hai; Bonnesen, Peter V.; Hong, Kunlun

doi:10.1039/c5qo00181a

Cited by 28 publications

(10 citation statements)

References 43 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Chemie dehalogenated by heating a solution of 6 in DMSO, Pd 2 (dba) 3 , HCOONa and P(t-Bu) 3 at 100 8C for 12 hours, affording chlorine-free PDI-integrated dehydro [20]annulene 11 in almost 50 % yields (Scheme 2). [19] These results confirmed that ortho-ethynyl substituted PDIs can be apt to achieve linearly-fused PDI oligomers bridged by 1,3-butadiyne-based macrocycles, and the resulting molecules might impart with excellent properties of PDI chromophores and unique macrocyclic topology.…”

Section: Methodssupporting

confidence: 63%

Monocyclic and Dicyclic Dehydro[20]annulenes Integrated with Perylene Diimide

et al. 2021

View full text Add to dashboard Cite

A novel kind of monocyclic and dicyclic dehydro[20]annulenes exhibiting specific sizes and topologies from regioselective unilateral ortho‐diethynyl PDI, is developed by Cu‐catalyzed Glaser–Hay homo‐coupling and cross‐coupling. Through the integration of electron‐deficient PDI chromophores into the dehydroannulene scaffolding, these macrocycles exhibit intense and characteristic absorption properties and the degenerated LUMO levels. The single‐crystal X‐ray diffraction analysis unambiguously revealed unique porous supramolecular structures, which display micropore characteristics with surface area of 120.74 m2 g−1. A moderate electron mobility of 0.05 cm2 V−1 s−1 for chlorine‐free dehydro[20]annulene based on micrometer‐sized single‐crystalline transistors was witnessed. The porous and yet semiconducting features signify the prospects of PDI‐integrated dehydroannulenes in organic optoelectronics.

show abstract

Section: Methodssupporting

confidence: 63%

Monocyclic and Dicyclic Dehydro[20]annulenes Integrated with Perylene Diimide

et al. 2021

View full text Add to dashboard Cite

show abstract

“…Owing to the mild reaction conditions, sensitive groups such as cyan, ester, amino, hydroxyl, aldehyde, and ketone are not affected (Table 1, 2h–2m ), in sharp contrast to current C–H/C–D exchange and early-stage C–X deuteration processes involving strong bases. The latter requires expensive deuterium sources (CD 3 OD 38 , DCOONa 39 ), harsh reaction conditions (e.g., BuLi at −78 °C) 40 and is disadvantaged by very narrow substrate scopes. Although the H/D exchange of -NH 2 and -OH groups happens in D 2 O inevitably, the influence on the deuteration of C–I bond is negligible (Table 1, 2h and 2i ).…”

Section: Resultsmentioning

confidence: 99%

Controllable deuteration of halogenated compounds by photocatalytic D2O splitting

et al. 2018

View full text Add to dashboard Cite

Deuterium labeling is of great value in organic synthesis and the pharmaceutical industry. However, the state-of-the-art C–H/C–D exchange using noble metal catalysts or strong bases/acids suffers from poor functional group tolerances, poor selectivity and lack of scope for generating molecular complexity. Herein, we demonstrate the deuteration of halides using heavy water as the deuteration reagent and porous CdSe nanosheets as the catalyst. The deuteration mechanism involves the generation of highly active carbon and deuterium radicals via photoinduced electron transfer from CdSe to the substrates, followed by tandem radicals coupling process, which is mechanistically distinct from the traditional methods involving deuterium cations or anions. Our deuteration strategy shows better selectivity and functional group tolerances than current C–H/C–D exchange methods. Extending the synthetic scope, deuterated boronic acids, halides, alkynes, and aldehydes can be used as synthons in Suzuki coupling, Click reaction, C–H bond insertion reaction etc. for the synthesis of complex deuterated molecules.

show abstract

“…successfully synthesized deuterium‐labeled aromatic and heteroaromatic compounds with yields above 98% via palladium‐catalyzed dehalogenative deuteration. The Br/D exchange reactions of arenes could also occur in a palladium‐catalyzed system with a deuterium‐labeled formate salt as the deuterium source [23] . Xia et al [24] .…”

Section: Conventional Deuteration Reactionmentioning

confidence: 99%

Recent Advances in the Synthesis of Deuterium‐Labeled Compounds

2021

View full text Add to dashboard Cite

Deuterium‐labeled compounds are of importance in chemical, environmental, and biological fields. Preparation methods for deuterium‐labeled compounds have been studied extensively in response to increasing demand for these chemicals. In this review, we summarize recent advances in synthetic methods and present a comprehensive overview of diverse routes, including conventional deuteration and hydrogen‐deuterium exchange. Deuteration by the classical process, which starts from appropriate available labeled precursors, is introduced for different reaction types. Key features of hydrogen‐deuterium exchange are elaborated in detail from the perspective of the catalyst and the chemical structure of the substrate. Regioselective deuteration at the target position is discussed because of the role of stereospecific deuterium labeling in medicine. Finally, challenges and future prospects of these processes are discussed to provide a general guideline for the synthesis of deuterium‐labeled compounds.

show abstract

Palladium-catalyzed Br/D exchange of arenes: selective deuterium incorporation with versatile functional group tolerance and high efficiency

Cited by 28 publications

References 43 publications

Monocyclic and Dicyclic Dehydro[20]annulenes Integrated with Perylene Diimide

Monocyclic and Dicyclic Dehydro[20]annulenes Integrated with Perylene Diimide

Controllable deuteration of halogenated compounds by photocatalytic D2O splitting

Recent Advances in the Synthesis of Deuterium‐Labeled Compounds

Contact Info

Product

Resources

About