- Sulfone–Metal Exchange and Alkylation of Sulfonylnitriles
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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.
- Yang, Xun,Nath, Dinesh,Gau, Michael R.,Steward, Omar W.,Fleming, Fraser F.
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p. 7257 - 7260
(2017/06/13)
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- Chemoselective Alkylations with N- and C-Metalated Nitriles
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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
- Yang, Xun,Nath, Dinesh,Fleming, Fraser F.
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supporting information
p. 4906 - 4909
(2015/10/12)
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- Arylthio-metal exchange of α-arylthioalkanenitriles
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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.
- Nath, Dinesh,Skilbeck, Melanie C.,Coldham, Iain,Fleming, Fraser F.
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- TEMPO-mediated aliphatic C-H Oxidation with Oximes and hydrazones
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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.
- Zhu, Xu,Wang, Yi-Feng,Ren, Wei,Zhang, Feng-Lian,Chiba, Shunsuke
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supporting information
p. 3214 - 3217
(2013/07/26)
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- Sulfinylnitriles: Sulfinyl-metal exchange-alkylation strategies
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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
- Nath, Dinesh,Fleming, Fraser F.
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p. 2023 - 2029
(2013/03/14)
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- Carbopalladation of nitriles: Synthesis of benzocyclic ketones and cyclopentenones via Pd-catalyzed cyclization of ω-(2-iodoaryl)alkanenitriles and related compounds
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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.
- Pletnev, Alexandre A.,Larock, Richard C.
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p. 9428 - 9438
(2007/10/03)
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- Synthesis of benzocyclic ketones via palladium-catalyzed cyclization of ω-(2-iodoaryl)alkanenitriles
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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
- Pletnev, Alexandre A.,Larock, Richard C.
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p. 2133 - 2136
(2007/10/03)
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- THE REDUCTIVE LITHIATION OF THIOACETALS, α,α-BIS(TRIMETHYLSILYL)-ALKYL SULFIDES, AND 2-ALKYL-2-ETHYLTHIOALKANENITRILES USING TRIBUTYLSTANNYLLITHIUM
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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.
- Takeda, Takeshi,Ando, Kazuo,Mamada, Akira,Fujiwara, Tooru
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p. 1149 - 1152
(2007/10/02)
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