Regio- and stereo-chemical features of the stannylcopper(I)-induced substitution in propargylic substrates

Ruitenberg, K.; Westmijze, H.; Meijer, J.; Elsevier, Cornelis J.; Vermeer, P.

doi:10.1016/s0022-328x(00)98533-4

Cited by 33 publications

(7 citation statements)

References 8 publications

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“…This high-field shift is caused by the strong shielding effect exerted by the (triphenyl)germyl group. It agrees well with 6('3CH3)-values for related silicon 191 and tin [7] substituted allenes.…”

Section: Methodssupporting

confidence: 83%

“…The synthesis of allenylstannanes following the R,SnLi as well as the allenylmagnesium halide route suffers from the same shortcomings mentioned for the germyl case [4,6]. Much better results were obtained in our laboratory by using a-allenyl silver(I) complexes [5] and the stannylcuprate-induced substitution of 2-propynylic esters [7]. In this paper, the organometal-mediated synthesis of both germyl-and stannylallenes from the propargylic chlorides Ph,MC%CR'R"Cl (M = Ge, Sn) is reported.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Convenient synthesis of (triphenyl)germyl and (triphenydstannyl substituted allenes

Ruitenberg

Westmijze

Kleijn

et al. 1984

Journal of Organometallic Chemistry

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Section: Methodssupporting

confidence: 83%

Section: Introductionmentioning

confidence: 99%

Convenient synthesis of (triphenyl)germyl and (triphenydstannyl substituted allenes

Ruitenberg

Westmijze

Kleijn

et al. 1984

Journal of Organometallic Chemistry

Self Cite

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“…Only when R1 causes much greater steric hindrance than R2 and R3 is the acetylenic product, R^^sCCR^iSnR^, formed. 359 The stereochemical course of the allene formation was found to be mainly, or exclusively, anti. A study of the reaction of Me3SnCu(Me2S) (XXII) and [Me3SnCuSPh]Li (XXIII) with a,/3-acetylenic N,Ndimethylamides (XXIV) shows (a) that the overall process can be controlled experimentally so as to produce either N,N-dimethyl-(E)-(XXV) or -(Z)-3-(trimethylstannyl)-2-alkenamides (XXVI), (b) that the initially formed intermediate derived from the interaction of XXIII and XXIV is significantly more stable than that obtained by the reaction of XXIII and a,/3acetylenic esters, and (c) that the intermediate produced by treating XXIV with XXII can be trapped with electrophiles other than a proton.…”

Section: Tin(ii)mentioning

confidence: 92%

Transition metal-tin chemistry

Holt¹,

Wilson²,

Nelson³

1989

Chem. Rev.

374

165

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“…Allenylstannanes and silanes are versatile building blocks in advanced organic synthesis and in natural product synthesis. − Although many excellent procedures for selective synthesis of these organometallic compounds are already available in the literature, − there is a considerable need to broaden the variety of available functionalized species. Allenylstannanes and silanes undergo highly stereoselective reactions with various aldehydes in the presence of Lewis acid catalysts to afford homopropargyl alcohol products .…”

Section: Synthetic Utility Of the Productsmentioning

confidence: 99%

Palladium Pincer Complex Catalyzed Stannyl and Silyl Transfer to Propargylic Substrates: Synthetic Scope and Mechanism

2005

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Pincer complex catalyzed substitution of various propargylic substrates could be achieved using tin- and silicon-based dimetallic reagents to obtain propargyl- and allenylstannanes and silanes. These reactions involving chloride, mesylate, and epoxide substrates could be carried out under mild conditions, and therefore many functionalities (such as COOEt, OR, OH, NR, and NAc) are tolerated. It was shown that pincer catalysts with electron-supplying ligands, such as NCN, SCS, and SeCSe complexes, display the highest catalytic activity. The catalytic substitution of secondary propargyl chlorides and primary propargyl chlorides with electron-withdrawing substituents proceeds with high regioselectivity providing the allenyl product. Opening of the propargyl epoxides takes place with an excellent stereo- and regioselectivity to give stereodefined allenylstannanes. Silylstannanes as dimetallic reagents undergo an exclusive silyl transfer to the propargylic substrate affording allenylsilanes with high regioselectivity. According to our mechanistic studies, the key intermediate of the reaction is an organostannane (or silane)-coordinated pincer complex, which is formed from the dimetallic reagent and the corresponding pincer complex catalyst. DFT modeling studies have shown that the trimethylstannyl functionality is transferred to the propargylic substrate in a single reaction step with high allenyl selectivity. Inspection of the TS structures reveals that the trimethylstannyl group transfer is initiated by the attack of the palladium-tin sigma-bond electrons on the propargylic substrate. This is a novel mechanism in palladium chemistry, which is based on the unique topology of the pincer complex catalysts.

show abstract

Regio- and stereo-chemical features of the stannylcopper(I)-induced substitution in propargylic substrates

Cited by 33 publications

References 8 publications

Convenient synthesis of (triphenyl)germyl and (triphenydstannyl substituted allenes

Convenient synthesis of (triphenyl)germyl and (triphenydstannyl substituted allenes

Transition metal-tin chemistry

Palladium Pincer Complex Catalyzed Stannyl and Silyl Transfer to Propargylic Substrates: Synthetic Scope and Mechanism

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