104367-54-6Relevant academic research and scientific papers
Sulfone–Metal Exchange and Alkylation of Sulfonylnitriles
Yang, Xun,Nath, Dinesh,Gau, Michael R.,Steward, Omar W.,Fleming, Fraser F.
, p. 7257 - 7260 (2017/06/13)
The first general sulfone–metal exchange is described. Treating substituted 2-pyridylsulfonylacetonitriles with either BuLi or Bu3MgLi generates metalated nitriles that efficiently intercept a variety of electrophiles to afford quaternary nitriles. The 2-pyridylsulfone is critical for the sulfone–metal exchange because chelation anchors the organometallic proximal to the electrophilic, tetrasubstituted sulfone to override complex-induced deprotonation. Alkylating commercial 2-pyridinesulfonylacetonitrile with mild bases, either K2CO3 or DBU, and subsequent sulfone–metal exchange and alkylation rapidly assembles quaternary nitriles by three alkylations, only one of which requires an organometallic reagent.
Chemoselective Alkylations with N- and C-Metalated Nitriles
Yang, Xun,Nath, Dinesh,Fleming, Fraser F.
supporting information, p. 4906 - 4909 (2015/10/12)
Metalated nitriles exhibit complementary chemoselectivities in electrophilic alkylations. N-Lithiated or C-magnesiated nitriles can be prepared from the same nitrile precursor and selectively reacted with a 1:1 mixture of methyl cyanoformate and benzyl br
Arylthio-metal exchange of α-arylthioalkanenitriles
Nath, Dinesh,Skilbeck, Melanie C.,Coldham, Iain,Fleming, Fraser F.
, p. 62 - 65 (2014/01/23)
The addition of BuLi, Bu3MgLi, Et2ZnBuLi, or Me 2CuLi to α-arylthioalkanenitriles triggers an arylthio-metal exchange. NMR spectroscopic analyses implicate organometallic attack on sulfur forming a three-coordinate sulfidate as the key intermediate. Electrophilic trapping affords tertiary and quaternary nitriles in high yield. The method addresses the challenge of improving the functional group tolerance and preventing polyalkylations.
Sulfinylnitriles: Sulfinyl-metal exchange-alkylation strategies
Nath, Dinesh,Fleming, Fraser F.
, p. 2023 - 2029 (2013/03/14)
Adding organolithiums, Grignard reagents, or zincates to sulfinylnitriles triggers a facile sulfinyl-metal exchange to afford N- or C-metalated nitriles. Sulfinyl-magnesium exchange-alkylations efficiently install quaternary and tertiary centers, even in
TEMPO-mediated aliphatic C-H Oxidation with Oximes and hydrazones
Zhu, Xu,Wang, Yi-Feng,Ren, Wei,Zhang, Feng-Lian,Chiba, Shunsuke
supporting information, p. 3214 - 3217 (2013/07/26)
A method for aliphatic C-H bond oxidation of oximes and hydrazones mediated by 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO) has been developed, which enables the concise assembly of substituted isoxazole and pyrazole skeletons.
Carbopalladation of nitriles: Synthesis of benzocyclic ketones and cyclopentenones via Pd-catalyzed cyclization of ω-(2-iodoaryl)alkanenitriles and related compounds
Pletnev, Alexandre A.,Larock, Richard C.
, p. 9428 - 9438 (2007/10/03)
An efficient procedure for the synthesis of 2,2-disubstituted benzocyclic ketones by intramolecular carbopalladation of nitriles has been developed. The cyclization of substituted 3-(2-iodoaryl)-propanenitriles affords indanones in high yields. The reaction is compatible with a wide variety of functional groups. This methodology has been extended to the synthesis of tetralones and cyclopentenones.
Synthesis of benzocyclic ketones via palladium-catalyzed cyclization of ω-(2-iodoaryl)alkanenitriles
Pletnev, Alexandre A.,Larock, Richard C.
, p. 2133 - 2136 (2007/10/03)
An efficient procedure for the synthesis of 2,2-disubstituted benzocyclic ketones by intramolecular carbopalladation of nitriles has been developed. The cyclization of substituted 3-(2-iodoaryl)propanenitriles affords indanones in high yields. The reactio
THE REDUCTIVE LITHIATION OF THIOACETALS, α,α-BIS(TRIMETHYLSILYL)-ALKYL SULFIDES, AND 2-ALKYL-2-ETHYLTHIOALKANENITRILES USING TRIBUTYLSTANNYLLITHIUM
Takeda, Takeshi,Ando, Kazuo,Mamada, Akira,Fujiwara, Tooru
, p. 1149 - 1152 (2007/10/02)
The reaction of thioacetals of phenyl ketones, α,α-bis(trimethylsilyl)alkyl sulfides, and 2-alkyl-2-ethylthioalkanenitriles with tributhylstannyllithium gave the corresponding α-anions of sulfides, α,α-bis(trimethylsilyl)alkane, and nitriles, respectively.
