Metalations With Organosodium Compounds

Benkeser, Robert A.; Foster, Donald J.; Sauve, Dale M.; Nobis, John F.

doi:10.1021/cr50017a002

Cited by 52 publications

(22 citation statements)

References 48 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Despite the synthetic promise of such species, the potential of multimetalation remains underutilized, even in organolithium chemistry 3,16,17,27,28 . Double sodiation via deprotonation has been reported 3,14,16,17,[29][30][31][32][33][34][35][36][37][38][39][40][41] , but efficient triple or quadruple sodiation has not been known to date. Our halogen-sodium exchange method enabled the regioselective access to tri-and tetrasodiated compounds (Fig.…”

Section: Resultsmentioning

confidence: 99%

Halogen–sodium exchange enables efficient access to organosodium compounds

et al. 2021

View full text Add to dashboard Cite

With sodium being the most abundant alkali metal on Earth, organosodium compounds are an attractive choice for sustainable chemical synthesis. However, organosodium compounds are rarely used—and are overshadowed by organolithium compounds—because of a lack of convenient and efficient preparation methods. Here we report a halogen–sodium exchange method to prepare a large variety of (hetero)aryl- and alkenylsodium compounds including tri- and tetrasodioarenes, many of them previously inaccessible by other methods. The key discovery is the use of a primary and bulky alkylsodium lacking β-hydrogens, which retards undesired reactions, such as Wurtz–Fittig coupling and β-hydrogen elimination, and enables efficient halogen–sodium exchange. The alkylsodium is readily prepared in situ from neopentyl chloride and an easy-to-handle sodium dispersion. We believe that the efficiency, generality, and convenience of the present method will contribute to the widespread use of organosodium in organic synthesis, ultimately contributing to the development of sustainable organic synthesis by rivalling the currently dominant organolithium reagents.

show abstract

Section: Resultsmentioning

confidence: 99%

Halogen–sodium exchange enables efficient access to organosodium compounds

et al. 2021

View full text Add to dashboard Cite

show abstract

“…Despite occasional bursts of activity through the last century, − organosodium chemistry has not kept abreast with organolithium chemistry by any measure. , The most reactive reagents such as sodium diisopropylamide (NaDA) and n -butylsodium that would logically be cornerstones of the discipline suffer from low solubility in inert hydrocarbon solvents and instability in ethereal solvents if not handled correctly . These were solvable problems, and serious progress toward developing convenient, highly reactive bases has been made. ,,− Given the lackluster interest from synthetic chemists, it follows that organosodium chemistry has received even less attention from those who care about structure and mechanism.…”

Section: Introductionmentioning

confidence: 99%

Reactions of Sodium Diisopropylamide: Liquid-Phase and Solid–Liquid Phase-Transfer Catalysis by N,N,N′,N″,N″-Pentamethyldiethylenetriamine

Woltornist

Algera

et al. 2021

J. Am. Chem. Soc.

View full text Add to dashboard Cite

Sodium diisopropylamide (NaDA) in N,N-dimethylethylamine (DMEA) and DMEA−hydrocarbon mixtures with added N,N,N′,N″,N″-pentamethyldiethylenetriamine (PMDTA) reacts with alkyl halides, epoxides, hydrazones, arenes, alkenes, and allyl ethers. Comparisons of PMDTA with N,N,N′,N′tetramethylethylenediamine (TMEDA) accompanied by detailed rate and computational studies reveal the importance of the trifunctionality and κ 2 −κ 3 hemilability. Rate studies show exclusively monomer-based reactions of 2-bromooctane, cyclooctene oxide, and dimethylresorcinol. Catalysis with 10 mol % PMDTA shows up to >30-fold accelerations (k cat > 300) with no evidence of inhibition over 10 turnovers. Solid−liquid phase-transfer catalysis (SLPTC) is explored as a means to optimize the catalysis as well as explore the merits of heterogeneous reaction conditions.

show abstract

“…5 f E/Z = 83/17 7 fd: 98% [c] Z/E > 99/1 3 5 c E/Z = 83/17 7 cl: 74% [b] Z/E > 99/1 9 5 g E/Z = 68/32 7 gc: 95% [c] Z/E > 99/1 4 5 d E/Z = 79/21 7 dm: 67% [c] E/Z > 99/1 10 5 g E/Z = 68/32 7 gl:91 % [b] Z/E > 99/1 5 5 d [d] E/Z = 79/21 7 de: 57% [b] E/Z > 99/1 11 5 h E/Z = 71/29 7 ho: 95% [c] E/Z = 77/23 [a] # SM product [a] 6 5 e [d] E/Z = 78/22…”

mentioning

confidence: 99%

“…However, the sodiation of such unsaturated compounds is much less explored. [4] Moreover, the use of sodium organometallics is of high interest due to the low price, high abundancy and low toxicity of sodium salts. [5] Recently, arylsodium compounds have been prepared by Collum using NaDA (sodium diisopropylamide) as deprotonating agent [4e,6] and by Asako and Takai, who have investigated the utility of arylsodiums in catalytic cross-couplings.…”

mentioning

confidence: 99%

Continuous Flow Sodiation of Substituted Acrylonitriles, Alkenyl Sulfides and Acrylates

et al. 2020

View full text Add to dashboard Cite

The sodiation of substituted acrylonitriles and alkenyl sulfides in a continuous flow setup using NaDA (sodium diisopropylamide) in EtNMe 2 or NaTMP (sodium 2,2,6,6-tetramethylpiperidide)•TMEDA in n-hexane provides sodiated acrylonitriles and alkenyl sulfides, which are subsequently trapped in batch with various electrophiles such as aldehydes, ketones, disulfides and allylic bromides affording functionalized acrylonitriles and alkenyl sulfides. This flowprocedure was successfully extended to other acrylates by using Barbier-type conditions.

show abstract

Metalations With Organosodium Compounds

Cited by 52 publications

References 48 publications

Halogen–sodium exchange enables efficient access to organosodium compounds

Halogen–sodium exchange enables efficient access to organosodium compounds

Reactions of Sodium Diisopropylamide: Liquid-Phase and Solid–Liquid Phase-Transfer Catalysis by N,N,N′,N″,N″-Pentamethyldiethylenetriamine

Continuous Flow Sodiation of Substituted Acrylonitriles, Alkenyl Sulfides and Acrylates

Contact Info

Product

Resources

About