Nucleophilic addition to transition metal complexes

The author's studies of nucleophilic addition, chiefly to cationic complexes of the hydrocarbon metal and hydrocarbon metal carbonyl types are reviewed and related to other work in the area. Effects studied include stereospecificity, regioselectivity, competition with substitution, and rearrangements.     

Nucleophilic addition of acetophenone to 1,4-diethynylbenzene

Russian Journal of Organic Chemistry -     

Nucleophilic addition of 2-hydroxyquinoxaline to acetylenes

Vinylation of 2-hydroxyquinoxaline affords either 2-vinyloxyquinoxaline or 1-vinyl-2-quinoxalone depending on the reaction conditions. The reactions of 2-hydroxyquinoxaline with 3-phenylprop-2-ynonitrile or 4-hydroxyalk-2-ynonitriles yield 3-phenyl-3-(quinoxalyl-2-oxy)prop-2-enonitrile or 4-hydroxy-3-(quinoxalyl-2-oxy)alk-2-enonitriles, respectively. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 738–741, April, 2000.     

Nucleophilic addition to the tricarbonyl(η-cycloheptadienylium)iron cation by alkoxide ions. Formation of carboalkoxy intermediates

Nucleophilic addition the title compound by alkoxide ions (OR^?) at 0°C proceeds via a red intermediate probably involving metal-nucleophile interaction, and subsequent formation of the carboalkoxy compound C₇H₉Fe(CO)₂(CO₂R). On raising the temperature, the latter compound rearranges spontaneously by a dissociative mechanism to give the corresponding 5-exo-ring compound C₇H₉ORFe(CO)₃.     

Nucleophilic addition of the thiocyanate ion to ferrocenyl-stabilised carbocations

The reaction of ferrocenylmethylcarbocations with the ambident thiocyanate ion produces only the isothiocyanate isomer.     

8 - 乙烯基嘌呤上的亲核加成和环加成反应

研究了8-乙烯基嘌呤与甲醇、苯硫酚和丙二酸二乙酯之间的亲核加成反应以及与环戊二烯之间的环加成反应。合成了8种未见报道的8位取代的嘌呤衍生物,结构均经^1^HNMR、^13^CNMR、^1^H-^1^HNOESY、MS和元素分析确证。     

Nucleophilic addition of hydroxymethyl-1,2,3-triazoles to multiple bonds

The addition of C- and N-hydroxymethyl-1,2,3-triazoles to the activated multiple bonds of acrylonitrile and benzoylacetylene was studied. The structures of the compounds obtained were proved by means of the PMR and IR spectra.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1417–1420, October, 1982.     

Nucleophilic addition to substituted 1H-4,5-dihydroimidazolium salts

1H-4,5-Dihydroimidazolium salts 1 react readily with nucleophilic reagents originating cyclic products which may be stable or become transformed into acyclic compounds maintaining the structural ethylenediamine unit. With methylmagnesium iodide compound 1e affords the expected imidazolidine, but in the case of substituted 1-aryl-3-methyl-2-phenyl salts 1b-d the N-aryl-N′-methylethylenediamines 3b-d and acetophenone ( 4 ) were isolated, the process representing the transfer of the C-2 unit to a nucleophilic carbon. With alkaline cyanides salts 1 react efficiently affording α,α-diaminonitriles 5 . In these compounds the cyano group may be readily substituted by nucleophiles (hydroxyl anion, species with nucleophilic carbon and reagents that act by hydride ion transfer), in a way similar to the salts but with better yields.     

Nucleophilic addition of nitriles to tertiary monocyclic terpenes alcohols

Previously unknown secondary amines have been synthesized by the Ritter reaction of p-menthan-8-ol with propio- and benzonitriles. The performance of this reaction with -terpeneol and benzonitrile led to the formation of a mixture of N-(p-menth-1-en-8-yl)benzamide and N,N-(p-menth-1,8-diyl)dibenzamide. A transdiamide was also obtained on the reaction of -terpineol with isovaleronitrile. The use of propionitrile as the nucleophile with -terpineol led to the formation of 2-ethyl-4,4,8-trimethyl-8-propionamido-3-azabicyclo[3.3.1]non-2-ene.Institute of Physical Organic Chemistry, Academy of Sciences of the Belorussian SSR, Minsk. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 235–240, March–April, 1987.     

Nucleophilic addition of heterocyclic amines to conjugated enyne ketones

Nucleophilic addition of secondary heterocyclic amines (morpholine, piperidine, and piperazine) to the double or triple bond of (E)-1,5-diarylpent-2-en-4-yn-1-ones is controlled by the kinetic and thermodynamic factor, respectively. The regioselectivity of the addition of piperazine to these enynones is determined by the substituent nature in the benzene rings. Conjugated ketones with electron-donating substituents take up piperazine molecule at the double bond, and those with electron-withdrawing groups, at the triple bond.     

Nucleophilic addition of phenol derivatives to methyl 1-nitrocyclopropanecarboxylates

Nucleophilic ring opening of methyl 1-nitrocyclopropanecarboxylates by phenol derivatives in the presence of Cs2CO3 is described. The reaction tolerates a variety of substituents on both the aromatic alcohol and the cyclopropane and affords the products in good yields (53-84%) and with complete preservation of the enantiomeric excess at C-4. The methodology was applied in an enantioselective synthesis of the norepinephrine reuptake inhibitor atomoxetine (Strattera).