Modular terpene synthesis enabled by mild electrochemical couplings

Harwood, Stephen J.; Palkowitz, Maximilian; Gannett, Cara N.; Perez, Jesus Paulo L.; Yao, Zhen; Sun, Lijie; Abruña, Héctor D.; Anderson, Scott L.; Baran, Phil S.

doi:10.1126/science.abn1395

Cited by 88 publications

(91 citation statements)

References 101 publications

(69 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…A dvances in Ni-based catalysis have enabled new C-C bond-forming methodologies that directly couple two C electrophiles in a net-reductive process without the need to preform a nucleophilic coupling partner (1)(2)(3)(4). The ubiquity of simple organohalides or other C electrophiles has caused Ni-catalyzed cross-electrophile coupling (XEC) to become one of the most common strategies for C-C coupling in industry, particularly to form C(sp 3 )-C(sp 2 ) bonds (5)(6)(7)(8)(9)(10)(11).…”

mentioning

confidence: 99%

Controlling Ni redox states by dynamic ligand exchange for electroreductive Csp3–Csp2 coupling

Hamby

LaLama

Sevov

2022

Science

106

View full text Add to dashboard Cite

Cross-electrophile coupling (XEC) reactions of aryl and alkyl electrophiles are appealing but limited to specific substrate classes. Here, we report electroreductive XEC of previously incompatible electrophiles including tertiary alkyl bromides, aryl chlorides, and aryl/vinyl triflates. Reactions rely on the merger of an electrochemically active complex that selectively reacts with alkyl bromides through 1e – processes and an electrochemically inactive Ni 0 (phosphine) complex that selectively reacts with aryl electrophiles through 2e – processes. Accessing Ni 0 (phosphine) intermediates is critical to the strategy but is often challenging. We uncover a previously unknown pathway for electrochemically generating these key complexes at mild potentials through a choreographed series of ligand-exchange reactions. The mild methodology is applied to the alkylation of a range of substrates including natural products and pharmaceuticals.

show abstract

mentioning

confidence: 99%

Controlling Ni redox states by dynamic ligand exchange for electroreductive Csp3–Csp2 coupling

Hamby

LaLama

Sevov

2022

Science

106

View full text Add to dashboard Cite

show abstract

“…Some frontier areas, such as C–H functionalization, photocatalysis and electrosynthesis, have not paid enough attention to the field of fragrances, compared to the progress of methodologies and applications for natural products, drugs and functional molecules. With the ability of efficient coupling and cyclization, these methods are expected to have broad and fruitful applications for fragrance manufacture in the next decade [ 160 , 161 , 162 , 163 , 164 ]. Advanced technologies, such as continuous flow and automated synthetic platforms, have emerged that greatly improve efficiency and reduce carbon release during fragrance production, but the field still has much room for development.…”

Section: Discussionmentioning

confidence: 99%

Synthesis of Cyclic Fragrances via Transformations of Alkenes, Alkynes and Enynes: Strategies and Recent Progress

Lin¹,

Huang²,

Ouyang³

et al. 2022

Molecules

View full text Add to dashboard Cite

With increasing demand for customized commodities and the greater insight and understanding of olfaction, the synthesis of fragrances with diverse structures and odor characters has become a core task. Recent progress in organic synthesis and catalysis enables the rapid construction of carbocycles and heterocycles from readily available unsaturated molecular building blocks, with increased selectivity, atom economy, sustainability and product diversity. In this review, synthetic methods for creating cyclic fragrances, including both natural and synthetic ones, will be discussed, with a focus on the key transformations of alkenes, alkynes, dienes and enynes. Several strategies will be discussed, including cycloaddition, catalytic cyclization, ring-closing metathesis, intramolecular addition, and rearrangement reactions. Representative examples and the featured olfactory investigations will be highlighted, along with some perspectives on future developments in this area.

show abstract

“…Baran and co-workers in 2022, reported the synthesis of terpenes using electrochemical milder reaction condition (Scheme 18). 32 This protocol for the synthesis of terpene was facilitated by electrochemically enabled nickel-catalyzed decarboxylative coupling reactions in presence of silver nanoparticle-modified electrodes. The mechanistic features of the silver nanoparticle-modified electrodes were well documented with the help of various spectroscopic as well as analytical methods.…”

Section: Alkyl-alkenyl C−c Couplingmentioning

confidence: 99%

Recent Developments in the Electroreductive Functionalization of Carbon–Halogen Bonds

Halder¹,

Mahanty²,

Sarkar³

2022

Synthesis

View full text Add to dashboard Cite

Electrochemical organic transformations have made enormous progress over the past decades owing to the idiosyncratic redox nature. Electrochemistry is globally acknowledged for its sustainability and environ friendliness and several well-known redox processes get a new exquisite touch without expelling chemical waste and toxic by-products. Apart from this, electrochemistry has adequate potential to steer numerous non-spontaneous reactions like cross-coupling, C−C bond cleavage, radical generation, directed C–H functionalization reactions etc. in a straightforward manner. Beyond the electrochemical oxidation reactions, electrochemical reductive transformations are also enriching in the last few years. Electrochemical reduction can be facilitated by using different strategies like using a sacrificial electrode, sacrificial reagent or can be accomplished in a divided cell. In this short review, different methods for the functionalization of C−halogen bonds, including detailed mechanistic approaches, are discussed. 1 Introduction 2 Different strategies for the electrochemical reduction 3 Functionalization of C−halogen bonds through electrochemical reduction 3.1 Electro-reductive hydrodehalogenation 3.2 Electro-reductive C−C coupling of organohalides 3.2.1 Aryl-aryl C−C coupling 3.2.2 Aryl-alkenyl C−C coupling 3.2.3 Aryl-alkyl C−C coupling 3.2.4 Alkyl-alkenyl C−C coupling 3.2.5 Alkyl-alkyl C−C coupling 3.3 Electro-reductive coupling of organohalides with carbonyls (C=O) 3.4 Electro-reductive coupling of organohalides with organoborones 4 Conclusion

show abstract

Modular terpene synthesis enabled by mild electrochemical couplings

Cited by 88 publications

References 101 publications

Controlling Ni redox states by dynamic ligand exchange for electroreductive Csp3–Csp2 coupling

Controlling Ni redox states by dynamic ligand exchange for electroreductive Csp3–Csp2 coupling

Synthesis of Cyclic Fragrances via Transformations of Alkenes, Alkynes and Enynes: Strategies and Recent Progress

Recent Developments in the Electroreductive Functionalization of Carbon–Halogen Bonds

Contact Info

Product

Resources

About