1078-71-3Relevant articles and documents
Single-step process for the reductive deoxygenation of unhindered alcohols
Myers,Movassaghi,Zheng
, p. 8572 - 8573 (1997)
-
New One-pot Cross-coupling Reaction between Grignard Reagents and Alkoxymethyldiphenylphosphonium Iodides in situ-Formed from Alcohols, Chlorodiphenylphosphine and Iodomethane
Shintou, Taichi,Kikuchi, Wataru,Mukaiyama, Teruaki
, p. 676 - 677 (2003)
A new one-pot cross-coupling reaction between Grignard reagents and alkoxymethyldiphenylphosphonium iodides, which were in situ-formed from nBuLi-treated alcohols, chlorodiphenylphosphine and iodomethane, proceeded smoothly to afford the corresponding coupling products in good to high yields.
Differentiating C-Br and C-Cl bond activation by using solvent polarity: Applications to orthogonal alkyl-alkyl negishi reactions
Hadei, Niloufar,Achonduh, George T.,Valente, Cory,O'Brien, Christopher J.,Organ, Michael G.
, p. 3896 - 3899 (2011)
A pot to share: A Calkyl-Cl bond can be rendered "dormant" or "active" in the Negishi alkyl-alkyl cross-coupling by a simple solvent polarity "switch" (see scheme). Adjustment from a 1:2 to a 2:1 solvent ratio of dimethylimidazolidinone: tetrahydrofuran enables orthogonal alkyl-alkyl Negishi cross-coupling strategies to be carried out on bifunctional bromochloroalkanes in one pot at room temperature.
A user-friendly, all-purpose Pd-NHC (NHC = N-heterocyclic carbene) precatalyst for the Negishi reaction: A step towards a universal cross-coupling catalyst
Organ, Michael G.,Avola, Stephanie,Dubovyk, Igor,Hadei, Niloufar,Kantchev, Eric Assen B.,O'Brien, Christopher J.,Valente, Gory
, p. 4749 - 4755 (2006)
We have developed the first user-friendly Negishi protocol capable of routinely cross-coupling all combinations of alkyl and aryl centers. The use of an easily synthesized, air stable, highly active, well-defined precatalyst PEPPSI-IPr (1; PEPPSI = pyridine-enhanced precatalyst preparation, stabilization and initiation; IPr = diisopropyl-phenylimidazolium derivative) substantially increases the scope, reliability, and ease-of-use of the Negishi reaction. All organohalides and routinely used pseudohalides were excellent coupling partners, with the use of chlorides, bromides, iodides, triflates, tosylates, and mesylates resulting in high yield of the coupled product. Furthermore, all reactions were performed by using general laboratory techniques, with no glove box necessary as the precatalyst was weighed and stored in air. Utilization of this methodology allowed for the easy synthesis of an assortment of sterically encumbered biaryls and druglike heteroaromatics, demonstrating the value of the PEPPSI-IPr system. Furthermore, this is also the first time Pd-NHC (NHC = N-heterocyclic carbene) methodology has surpassed the related phosphine-ligated Negishi processes both in activity and use.
-
Vasil'eva,E.I.,Freidlina,R.Kh.
, (1961)
-
Thiol-Catalyzed Radical Decyanation of Aliphatic Nitriles with Sodium Borohydride
Kawamoto, Takuji,Oritani, Kyohei,Curran, Dennis P.,Kamimura, Akio
, p. 2084 - 2087 (2018)
Radical decyanation of aliphatic nitriles was achieved in the presence of NaBH4 and a thiol. The reaction proceeds via a radical mechanism involving borane radical anion addition to nitrile to form an iminyl radical, which undergoes carbon-carbon cleavage. Reductive radical addition to acrylonitrile is followed by decyanation to give a two-carbon homologated product in a net radical ethylation reaction.
Ni-Catalyzed Aryl Sulfide Synthesis through an Aryl Exchange Reaction
Isshiki, Ryota,Kurosawa, Miki B.,Muto, Kei,Yamaguchi, Junichiro
, p. 10333 - 10340 (2021/07/21)
A Ni-catalyzed aryl sulfide synthesis through an aryl exchange reaction between aryl sulfides and a variety of aryl electrophiles was developed. By using 2-pyridyl sulfide as a sulfide donor, this reaction achieved the synthesis of aryl sulfides without using odorous and toxic thiols. The use of a Ni/dcypt catalyst capable of cleaving and forming aryl-S bonds was important for the aryl exchange reaction between 2-pyridyl sulfides and aryl electrophiles, which include aromatic esters, arenol derivatives, and aryl halides. Mechanistic studies revealed that Ni/dcypt can simultaneously undergo oxidative additions of aryl sulfides and aromatic esters, followed by ligand exchange between the generated aryl-Ni-SR and aryl-Ni-OAr species to furnish aryl exchanged compounds.
Hydrodecyanation of Secondary Alkyl Nitriles and Malononitriles to Alkanes using DiMeImd-BH3
Kawamoto, Takuji,Oritani, Kyohei,Kawabata, Atsushi,Morioka, Tsubasa,Matsubara, Hiroshi,Kamimura, Akio
, p. 6137 - 6142 (2020/05/22)
The decyanation of secondary aliphatic nitriles and the 2-fold decyanation of malononitriles leading to alkanes in the presence of 1,3-dimethylimidazol-2-ylidene borane (diMeImd-BH3) are reported. These reactions proceed via a radical mechanism that involves the addition of a borane radical to the nitrile to form an iminyl radical, followed by cleavage of a carbon-carbon bond. Theoretical calculations suggest that the β-cleavage of these iminyl radicals, which affords NHC-BH2CN and the corresponding alkyl radicals, is the rate-determining step in this reaction.
