- Iron-Catalyzed Isopropylation of Electron-Deficient Aryl and Heteroaryl Chlorides
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Traditional methods for the preparation of secondary alkyl-substituted aryl and heteroaryl chlorides challenge both selectivity and functional group tolerance. This contribution describes the use of statistical design of experiments to develop an effective procedure for the preparation of isopropyl-substituted (hetero)arenes with minimal isopropyl to n-propyl isomerization. The reaction tolerates electronically diverse aryl chloride coupling partners, with excellent conversion observed for strongly electron-deficient aromatic rings, such as esters and amides. Electron-rich systems, including methyl- and methoxy-substituted aryl chlorides, were found to be less reactive. Furthermore, the reaction was found to be most successful when heteroaryl chlorides were submitted to the cross-coupling protocol. By mapping substituent effects on reaction selectivity, we were able to show that electron-deficient aryl chlorides are essential for efficient coupling, and use electronic structure calculations to predict the likelihood of successful coupling through the estimation of the electron affinity of each aryl chloride. Moderate isolated yields were achieved with selected aryl chlorides, and moderate to good isolated yields were obtained for all the heteroaryl chlorides coupled. Excellent selectivity was observed when a 2,6-dichloroquinoline was used, allowing mono-substitution on a challenging substrate. (Figure presented.).
- Sanderson, James N.,Dominey, Andrew P.,Percy, Jonathan M.
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supporting information
p. 1007 - 1017
(2017/03/27)
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- COMPOUNDS AS HSP90 INHIBITORS
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The invention provides novel compounds of formula (I) wherein: one of the a, b, c or d members is a nitrogen atom and the remaining members are carbon atoms; and R3 is a radical selected from the group consisting of: —S—R14 and —CH2—R15. The compounds of formula (I) are useful for treating diseases mediated by a heat shock protein 90 (Hsp 90)
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Page/Page column 70
(2009/03/07)
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- Reductive one-carbon homologation of aldehydes and ketones
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A rhodium-catalyzed methylenation-hydrogenation cascade process allows the homologation of carbonyl compounds to lead to the corresponding alkanes in high yields.
- Lebel, Helene,Ladjel, Chehla
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p. 10159 - 10161
(2007/10/03)
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- 2-SACCHARINYLMETHYL PHOSPHATES, PHOSPHONATES AND PHOSPHINATES USEFUL AS PROTEOLYTIC ENZYME INHIBITORS AND COMPOSITIONS AND METHOD OF USE THEREOF
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4-R 1-R 2-R 3-2-Saccharinylmethyl and 4,7-C-4,5, 6,7-tetrahydro-2-saccharinylmethyl phosphates, phosphonates and phosphinates of formulas I and IIA respectively herein, useful in the treatment of degenerative diseases, and compositions containing them, methods for using them to treat degenerative diseases, and processes for their preparation by reaction of the corresponding 2-halomethylsaccharins with a phosphate, phosphonate or phosphinic acid of formula III herein in the presence of an acid-acceptor.
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- 2-SACCHARINYLMETHYL AND 4,5,6,7-TETRAHYDRO-2-SACCHARINYLMETHYL PHOSPHATES, PHOSPHONATES AND PHOSPHINATES USEFUL AS PROTEOLYTIC ENZYME INHIBITORS AND COMPOSITIONS AND METHOD OF USE THEREOF
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4-R 1-R 2-R 3-2-Saccharinylmethyl, 4-R 4-4-R 5-6-R 6-4,5,6,7-tetrahydro-2-saccharinylmethyl and 4,7-C-4,5, 6,7-tetrahydro-2-saccharinylmethyl phosphates, phosphonates and phosphinates of formulas I, II and IIA respectively herein, useful in the treatment of degenerative diseases, and compositions containing them, methods for using them to treat degenerative diseases, and processes for their preparation by reaction of the corresponding 2-halomethylsaccharins with a phosphate, phosphonate or phosphinic acid of formula III herein in the presence of an acid-acceptor.
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