Direct formation of functionalized and allylic organocopper reagents derived from a cuprous cyanide lithium bromide complex

Stack, Douglas E.; Dawson, Bryan T.; Rieke, Reuben D.

doi:10.1021/ja00012a041

Cited by 50 publications

(3 citation statements)

References 3 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[16][17][18] Toward weakly activated carbon-heteroatom bonds, the use of copper as a reducing reagent was limited probably because of its ability to produce oxide layers. However, recent improvements made the elaboration of reactive Cu ‫ء‬ species possible 19 in particular by chemical reduction of Cu I -based phosphine complexes. The point in using copper is its ability to give C-Cu I functions with nonactivated organic chlorides and bromides.…”

mentioning

confidence: 99%

Reactivity of Long Chain α,ω-Dibromoalkanes at Palladized Solid Cathodes: Homocoupling vs Oligomerization

Jouikov¹,

Poizot²,

Simonet³

2009

J. Electrochem. Soc.

View full text Add to dashboard Cite

Copper-palladium ͑Cu-Pd͒ and silver-palladium ͑Ag-Pd͒ systems are used as cathode materials for reducing long chain ␣,-dibromoalkanes ͓Br-͑CH 2 ͒ n -Br͔ with n Ͼ 3. Such interfaces globally permit the cleavage of the two C-Br bonds in a single two-electron process. A spectacular potential shift ͑⌬E͒ is obtained in comparison with glassy carbon electrodes at which the total reduction corresponds to a four-electron process. Such potential shifts are typically of the order of 1 V. In particular, cathodic reactions are easily achieved at Ag-Pd interfaces. Under these conditions, supporting evidences are given for the formation ͑according to simultaneous or sequenced processes͒ of a transient ␣,-biradical with different lengths of the alkyl chain ͑6 Ͻ n Ͻ 12͒. Macroelectrolysis data show that palladized interface reactions give rise to heterogeneous couplings and, markedly, the formation of homodimers. Reductions of ␣,-dibromoalkanes in the presence of copper-palladium, palladium, and silverpalladium fine powders efficiently induce the deposit of Cu, Pd, and Ag nanoparticles at chemically inactive electrified surfaces ͑glassy carbon and graphite͒.

show abstract

mentioning

confidence: 99%

Reactivity of Long Chain α,ω-Dibromoalkanes at Palladized Solid Cathodes: Homocoupling vs Oligomerization

Jouikov¹,

Poizot²,

Simonet³

2009

J. Electrochem. Soc.

View full text Add to dashboard Cite

show abstract

“…Compound 20 decomposed completely at room temperature within 6 h; in the 31 P NMR spectrum, two new signals appeared around 55 ppm and one at 37 ppm. In an alternative approach, 20 was obtained by reaction of 12 with in situ prepared, highly reactive metallic copper, in analogy with a procedure developed by Rieke . A 31 P NMR spectrum of the crude reaction mixture showed the presence of 20 (δ( 31 P) 171 ppm, 1 J (PW) = 244 Hz), 7 , and a component with δ( 31 P) 227 ppm, in a ratio of 10.6:1:2.6.…”

Section: Resultsmentioning

confidence: 99%

“…Synthesis of 20 via 12. The highly reactive Cu(0) was prepared by dropwise addition of a solution of CuCN·2LiBr (1.0 mmol) in THF (1 mL) to lithium naphthalenide (1.1 mmol) in THF (2 mL) at −100 °C. After 5 min stirring at −100 °C, a solution of 12 (0.25 mmol) in THF (0.6 mL) was added dropwise.…”

Section: Methodsmentioning

confidence: 99%

Reactivity of Organozinc Derivatives of Phosphinines

Teunissen

Bickelhaupt

1996

Organometallics

View full text Add to dashboard Cite

The reactions of the 2-organozinc derivatives 1, 2, and 3 of 4,5-dimethylphosphinine with electrophiles of phosphorus, arsenic, tin, copper, silver, and mercury are discussed. The reactions of 2 and 3 with arsenic trichloride furnished the monosubstitution products 4 and 5, respectively, which were not isolable in pure form. Reactions of 2 and 3 with phosphorus electrophiles were partially successful, but the monosubstitution products 8 and 11, respectively, were not formed selectively; among the byproducts were 7, 9, and 10. Transmetalation reactions with tin electrophiles gave 13 (37%) and 16 (7%), which were isolated in pure form. Transmetalation of 2 with a copper salt furnished copper derivative 17, which was trapped below −80 °C with a Michael acceptor and chlorotrimethylsilane to give the 1,4-addition product 19. This compound was obtained in nearly pure form in a yield of 20% relative to the 2-iodophosphinine 10. Transmetalation of 3 with a copper salt furnished the copper derivative 20, which decomposed within 6 h at room temperature. This compound was also prepared via direct insertion of reactive Cu(0) into 12. Transmetalations with silver salts afforded the organosilver derivatives 21−21‘ ‘. These silver species turned out to be rather unstable at room temperature. Transmetalation reactions with mercury salts were successful with 1, 2, and 3. The organomercury derivative 22 obtained via 1 and 2, respectively, decomposed at room temperature, but was characterized by 1H, 13C, and 31P NMR spectroscopies. The relatively stable organomercury derivative 23, obtained from 3, was isolated in a yield of 50% relative to 10.

show abstract

Allylcopper

Linderman¹

2001

Encyclopedia of Reagents for Organic Synthesis

View full text Add to dashboard Cite

Direct formation of functionalized and allylic organocopper reagents derived from a cuprous cyanide lithium bromide complex

Cited by 50 publications

References 3 publications

Reactivity of Long Chain α,ω-Dibromoalkanes at Palladized Solid Cathodes: Homocoupling vs Oligomerization

Reactivity of Long Chain α,ω-Dibromoalkanes at Palladized Solid Cathodes: Homocoupling vs Oligomerization

Reactivity of Organozinc Derivatives of Phosphinines

Allylcopper

Contact Info

Product

Resources

About