Transition metal catalysed cross-coupling between benzylic halides and aryl nucleophiles. Synthesis of some toxicologically interesting tetrachlorobenzyltoluenes.

Lang, Robert-Jan de; Hooijdonk, M. J. C. M. Van; Brandsma, L.; Kramer, Hester; Seinen, Willem

doi:10.1016/s0040-4020(98)83030-5

Cited by 44 publications

(15 citation statements)

References 26 publications

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“…1 H NMR spectra were measured at 300 MHz and 13 C NMR spectra were measured at 75 MHz in CDCl 3 or in C 6 D 6 with TMS as the internal standard. Acetylenic sulfones37 and organozinc reagents38, 39 were prepared according to literature procedures.…”

Section: Methodsmentioning

confidence: 99%

Regio‐ and stereospecific synthesis of polysubstituted alkenes by carbozincation of acetylenic sulfones

Xie

Wang

et al. 2009

Applied Organom Chemis

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Section: Methodsmentioning

confidence: 99%

Regio‐ and stereospecific synthesis of polysubstituted alkenes by carbozincation of acetylenic sulfones

Xie

Wang

et al. 2009

Applied Organom Chemis

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“…benzylation of 1a was achieved using 10% CuBr 12 leading to the corresponding product 6d in 85% yield (entry 4). Quenching of zinc intermediates of type 4 with less reactive electrophiles such as an aldehyde provided low yields.…”

Section: Syn Thesismentioning

confidence: 99%

Zincation and Magnesiation of Functionalized Silylated Cyanohydrins Using TMP-Bases

Castelló-Micó

Knöchel

2017

Synthesis

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Polyfunctional silylated cyanohydrins are readily magnesiated or zincated with TMPMgCl·LiCl or TMP2Zn·2MgCl2·2LiCl leading to the corresponding metallated derivatives. These Mg- or Zn-derivatives react with various electrophiles such as benzylic bromides, allylic bromides, acid chlorides, aldehydes, NCCO2Et, or MeSO2SMe. Subsequently, TBAF-deprotection provides the corresponding keto or 1,2-diketo derivatives.

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“…Aromatic sulfonamides, in turn, were obtained in a three-step procedure starting from commercially available benzenesulfonyl chloride. Ethyl and benzyl groups were introduced in ortho position via metallation-alkylation [13] and Negishi cross-coupling [14], respectively, starting from N-(tert-butyl)benzenesulfonamide (2) [15] ( 3 3a and 3b, resp. ; Scheme 2).…”

mentioning

confidence: 99%

Intramolecular Asymmetric Amidations of Sulfonamides and Sulfamates Catalyzed by Chiral Dirhodium(II) Complexes

Fruit

Müller

2004

Helvetica Chimica Acta

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Enantioselective intramolecular amidation of aliphatic sulfonamides was achieved for the first time by means of chiral carboxylatodirhodium(II) catalysts in conjunction with PhI(OAc) 2 and MgO in high yields and with enantioselectivities of up to 66% (Scheme 3, Table 1 isoquinoline-2-acetato). In addition, these carboxylatodirhodium(II) catalysts were also efficient in intramolecular amidations of aliphatic sulfamates esters, although the enantioselectivity of these latter reactions was significantly lower (Scheme 4, Table 3).Introduction. ± Amidation of saturated CÀH bonds and aziridination of olefins catalyzed by metal complexes based on Fe, Mn, Ru, Cu, or Rh are established methodologies for CÀN bond-formation [1] and, consequently, for the synthesis of amine derivatives. Some years ago, the Rh II -catalyzed aziridination [2] and sulfonamidation [3] with phenyliodinanes derived from aromatic sulfonamides has been investigated in our group. The reactions exhibited features analogous to the corresponding metal-catalyzed carbene-transfer reactions [4]. The aziridination was found to be stereospecific, except in the case of stilbene, and the amidation proceeded with retention of configuration at the reacting C-atom, indicating intervention of a metal-complexed nitrene, in analogy to the corresponding intermediate metallocarbenes resulting from decomposition of diazo compounds with Rh II catalysts. Some preliminary experiments showed that the system was suitable for asymmetric nitrene transfer. However, it suffered several shortcomings. Owing to the requirement of aromatic sulfonamides as precursors for the phenyliodinanes [5], the possibilities of carrying out intramolecular aziridinations and/or amidations [6] appeared very limited. In addition, a large excess of substrate was necessary in the case of intermolecular reactions to achieve satisfactory yields, while reactions carried out with an excess of reagent over the substrate produced unsatisfactory results. Finally, some reactions, in particular intermolecular amidations, proceeded very sluggishly and resulted in decomposition of the phenyliodinanes to afford sulfonamides without generation of the expected products of nitrene insertion.The transition-metal-catalyzed nitrene transfer has been further developed by other groups. Dodd, Dauban, and co-workers reported that, contrary to the traditional opinion [7], phenyliodinanes derived from aliphatic sulfonamides are isolable and may be used for nitrene-transfer reactions [8]. In addition, they found conditions allowing

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Transition metal catalysed cross-coupling between benzylic halides and aryl nucleophiles. Synthesis of some toxicologically interesting tetrachlorobenzyltoluenes.

Cited by 44 publications

References 26 publications

Regio‐ and stereospecific synthesis of polysubstituted alkenes by carbozincation of acetylenic sulfones

Regio‐ and stereospecific synthesis of polysubstituted alkenes by carbozincation of acetylenic sulfones

Zincation and Magnesiation of Functionalized Silylated Cyanohydrins Using TMP-Bases

Intramolecular Asymmetric Amidations of Sulfonamides and Sulfamates Catalyzed by Chiral Dirhodium(II) Complexes

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Transition metal catalysed cross-coupling between benzylic halides and aryl nucleophiles. Synthesis of some toxicologically interesting tetrachlorobenzyltoluenes.

Cited by 44 publications

References 26 publications

Regio‐ and stereospecific synthesis of polysubstituted alkenes by carbozincation of acetylenic sulfones

Regio‐ and stereospecific synthesis of polysubstituted alkenes by carbozincation of acetylenic sulfones

Zincation and Magnesiation of Functionalized Silylated Cyano­hydrins Using TMP-Bases

Intramolecular Asymmetric Amidations of Sulfonamides and Sulfamates Catalyzed by Chiral Dirhodium(II) Complexes

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Zincation and Magnesiation of Functionalized Silylated Cyanohydrins Using TMP-Bases