France Gail - Academia.edu (original) (raw)
Papers by France Gail
![Research paper thumbnail of ChemInform Abstract: A Straightforward Synthesis of Pyridopyrazino[2,3-b]indoles and Indolo[2,3-b]quinoxaline](https://attachments.academia-assets.com/116226220/thumbnails/1.jpg)
](ChemInform, May 24, 2010
Halogen compounds P 0030 A Straightforward Synthesis of Alkenyl Nonaflates from Carbonyl Compound... more Halogen compounds P 0030 A Straightforward Synthesis of Alkenyl Nonaflates from Carbonyl Compounds Using Nonafluorobutane-1-sulfonyl Fluoride in Combination with Phosphazene Bases.-A general chemo-and regioselective synthesis of alkenyl nonaflates uses purified fluoride (II) and a phosphazene base. The regioselectivity of the process [e.g. for (VIII)] can be significantly influenced by the type of phosphazene base.-(VOGEL,
Synthesis, 2004
A selective way to obtain disubstituted 1,2,4-triazines in good yields by combining addition reac... more A selective way to obtain disubstituted 1,2,4-triazines in good yields by combining addition reactions and palladium-catalyzed cross-coupling reactions of organometallics with 3-methylsulfanyl-1,2,4-triazine is described.
Journal of the American Chemical Society, 2006
Enols, metal enolates, and enamines are the most important carbon nucleophiles in both biological... more Enols, metal enolates, and enamines are the most important carbon nucleophiles in both biological and chemical synthesis. 1 Many useful reactions owe their efficiency to selective formation of E or Z metal enolates (Figure 1). In contrast, the chemistry of enamines is limited to reactions of the E-isomers. The reason is simple: a classical condensation between an amine and a carbonyl compound is an equilibrium process that affords the thermodynamically more stable E-isomer. Transition-metal-catalyzed approaches to enamines include metal-catalyzed isomerization of N-allylamines, 2 amination of alkenyl halides, 3 hydroamination of alkynes, 4 and oxidative amination of olefins. 5 Likewise, all of these methods give the thermodynamic product. There are no useful, kinetically controlled, reactions that result in Z-enamine formation. Although strong base-promoted isomerization of N-allylamines to Z-enamines have been reported, 6 attempts to isolate the Z-product result in Z-toE isomerization and/or hydrolysis. The present contribution examines an unexpected rhodium-catalyzed route to chromatographically stable Z-enamines from N-allylaziridines. Since the aziridine ring is widely considered to be a stepping stone to other amines via diverse ring-opening processes, 7 this chemistry may find useful synthetic applications. Table 2. Substrate Scope for Isomerization of N-Allylaziridines to N-Alkenylaziridines with RhH(CO)(PPh3)3 Catalyst a a [Substrate]) 0.7 M, [substrate]/[Rh]) 66 at-78°C in THF under nitrogen. b Determined by GC. c [Substrate]/[Rh]) 10 at 60°C, 72 h. d [Substrate]/[Rh]) 20 at 60°C, 24 h. e [Substrate]/[Rh]) 66 at 20°C, 24 h. f Only the starting material was recovered.
Chemistry - A European Journal, 2008
In the presence of rhodium(I) hydride catalysts, tertiary N-allylamines are known to isomerise in... more In the presence of rhodium(I) hydride catalysts, tertiary N-allylamines are known to isomerise into E enamines. In contrast, we have recently found that N-allylaziridines isomerise to form Z enamines. On the basis of literature data, the most likely mechanism of isomerisation would involve a rhodium hydride addition/beta-hydride elimination sequence. We show that the observed selectivity cannot be adequately explained by this pathway and is more consistent with initial CH-activation followed by rearrangement to form a five-membered cyclometallated rhodium intermediate. This intermediate subsequently undergoes reductive elimination to form a C--H bond. The resulting geometrically stable Z enamines are useful building blocks for stereoselective synthesis.
Synlett, 2002
... triazines. France-Aimée Alphonse a,b , Franck Suzenet a , Anne Keromnes b , Bruno Lebret b , ... more ... triazines. France-Aimée Alphonse a,b , Franck Suzenet a , Anne Keromnes b , Bruno Lebret b , Gérald Guillaumet* a. ... 1997. 2b Drew MGB, Guillaneux D, Hudson MJ, Iveson PB, Russell ML, Madic C,Inorg. Chem. Commun. 2001, 4: 12. ...
ChemInform, May 24, 2010
Halogen compounds P 0030 A Straightforward Synthesis of Alkenyl Nonaflates from Carbonyl Compound... more Halogen compounds P 0030 A Straightforward Synthesis of Alkenyl Nonaflates from Carbonyl Compounds Using Nonafluorobutane-1-sulfonyl Fluoride in Combination with Phosphazene Bases.-A general chemo-and regioselective synthesis of alkenyl nonaflates uses purified fluoride (II) and a phosphazene base. The regioselectivity of the process [e.g. for (VIII)] can be significantly influenced by the type of phosphazene base.-(VOGEL,
Synthesis, 2004
A selective way to obtain disubstituted 1,2,4-triazines in good yields by combining addition reac... more A selective way to obtain disubstituted 1,2,4-triazines in good yields by combining addition reactions and palladium-catalyzed cross-coupling reactions of organometallics with 3-methylsulfanyl-1,2,4-triazine is described.
Journal of the American Chemical Society, 2006
Enols, metal enolates, and enamines are the most important carbon nucleophiles in both biological... more Enols, metal enolates, and enamines are the most important carbon nucleophiles in both biological and chemical synthesis. 1 Many useful reactions owe their efficiency to selective formation of E or Z metal enolates (Figure 1). In contrast, the chemistry of enamines is limited to reactions of the E-isomers. The reason is simple: a classical condensation between an amine and a carbonyl compound is an equilibrium process that affords the thermodynamically more stable E-isomer. Transition-metal-catalyzed approaches to enamines include metal-catalyzed isomerization of N-allylamines, 2 amination of alkenyl halides, 3 hydroamination of alkynes, 4 and oxidative amination of olefins. 5 Likewise, all of these methods give the thermodynamic product. There are no useful, kinetically controlled, reactions that result in Z-enamine formation. Although strong base-promoted isomerization of N-allylamines to Z-enamines have been reported, 6 attempts to isolate the Z-product result in Z-toE isomerization and/or hydrolysis. The present contribution examines an unexpected rhodium-catalyzed route to chromatographically stable Z-enamines from N-allylaziridines. Since the aziridine ring is widely considered to be a stepping stone to other amines via diverse ring-opening processes, 7 this chemistry may find useful synthetic applications. Table 2. Substrate Scope for Isomerization of N-Allylaziridines to N-Alkenylaziridines with RhH(CO)(PPh3)3 Catalyst a a [Substrate]) 0.7 M, [substrate]/[Rh]) 66 at-78°C in THF under nitrogen. b Determined by GC. c [Substrate]/[Rh]) 10 at 60°C, 72 h. d [Substrate]/[Rh]) 20 at 60°C, 24 h. e [Substrate]/[Rh]) 66 at 20°C, 24 h. f Only the starting material was recovered.
Chemistry - A European Journal, 2008
In the presence of rhodium(I) hydride catalysts, tertiary N-allylamines are known to isomerise in... more In the presence of rhodium(I) hydride catalysts, tertiary N-allylamines are known to isomerise into E enamines. In contrast, we have recently found that N-allylaziridines isomerise to form Z enamines. On the basis of literature data, the most likely mechanism of isomerisation would involve a rhodium hydride addition/beta-hydride elimination sequence. We show that the observed selectivity cannot be adequately explained by this pathway and is more consistent with initial CH-activation followed by rearrangement to form a five-membered cyclometallated rhodium intermediate. This intermediate subsequently undergoes reductive elimination to form a C--H bond. The resulting geometrically stable Z enamines are useful building blocks for stereoselective synthesis.
Synlett, 2002
... triazines. France-Aimée Alphonse a,b , Franck Suzenet a , Anne Keromnes b , Bruno Lebret b , ... more ... triazines. France-Aimée Alphonse a,b , Franck Suzenet a , Anne Keromnes b , Bruno Lebret b , Gérald Guillaumet* a. ... 1997. 2b Drew MGB, Guillaneux D, Hudson MJ, Iveson PB, Russell ML, Madic C,Inorg. Chem. Commun. 2001, 4: 12. ...