91076-08-3Relevant academic research and scientific papers
Total Synthesis of Leiodermatolide A via Transfer Hydrogenative Allylation, Crotylation, and Propargylation: Polyketide Construction beyond Discrete Allyl- or Allenylmetal Reagents
Krische, Michael J.,Roane, James,Siu, Yuk-Ming
supporting information, p. 10590 - 10595 (2021/07/28)
The total synthesis of leiodermatolide A was accomplished in 13 steps (LLS). Transfer hydrogenative variants of three carbonyl additions that traditionally rely on premetalated reagents (allylation, crotylation, and propargylation) are deployed together i
Synthesis of allenylzinc reagents by 1,2-rearrangement of alkynyl(disilyl)zincates derived from acetylenic epoxides and acetylenic aziridines
Bochatay, Valentin N.,Debien, Laurent,Chemla, Fabrice,Ferreira, Franck,Jackowski, Olivier,Perez-Luna, Alejandro
, p. 609 - 616 (2017/05/24)
Lithium alkynyl(disilyl)zincates obtained from metalated ethynyloxiranes, as well as from N-tert-butanesulfinyl(ethynyl)aziridines or N-tert-butanesulfonyl(ethynyl)aziridines, undergo 1,2-migration of the organosilyl group with ring opening of the oxirane or aziridine ring by SNi displacement. A developed protocol that involves nBuLi for the metalation step offers a straightforward approach to the corresponding δ-oxy- and δ-amino α-silyl allenylzinc intermediates. The reagents derived from the epoxides are amenable to subsequent in situ condensation with aldehydes or ketones to provide 1,3-diols but not those derived from aziridines that only react sluggishly in similar condensations.
Stereodivergent Silylzincation of α-Heteroatom-Substituted Alkynes
Fopp, Carolin,Romain, Elise,Isaac, Kevin,Chemla, Fabrice,Ferreira, Franck,Jackowski, Olivier,Oestreich, Martin,Perez-Luna, Alejandro
supporting information, p. 2054 - 2057 (2016/06/01)
Zinc reagents (Me2PhSi)2Zn and [(Me3Si)3Si]2Zn undergo highly regio- and stereoselective addition across the carbon-carbon triple bond of nitrogen-, sulfur-, oxygen-, and phosphorus-substituted termin
Asymmetric catalysis with silicon-based cuprates: Enantio- and regioselective allylic substitution of linear precursors
Hensel, Alexander,Oestreich, Martin
supporting information, p. 9062 - 9065 (2015/06/16)
An enantio- and regioselective allylic silylation of linear allylic phosphates that makes use of catalytically generated cuprate-type silicon nucleophiles is reported. The method relies on soft bis(triorganosilyl) zincs as silicon pronucleophiles that are prepared in situ from the corresponding hard lithium reagents by transmetalation with ZnCl2. With a preformed chiral N-heterocyclic carbene-copper(I) complex as catalyst, exceedingly high enantiomeric excesses are achieved. The new method is superior to existing ones using a silicon-boron reagent as the source of the silicon nucleophile. Zinc about it: Cuprates catalytically generated from bis(triorganosilyl)zinc compounds and a preformed chiral N-heterocyclic carbene-copper(I) complex allow for the highly enantio- and regioselective allylic silylation of various allylic phosphates. The method is broadly applicable with regard to the silicon pronucleophile and the allylic acceptor. It is the first example of asymmetric catalysis with a silicon-based cuprate.
Preparation and structural characterization of trimethylsilyl-substituted germylzinc halides, (Me3Si)3GeZnX (X = Cl, Br, and I) and silylzinc chloride, R(Me3Si)2SiZnCl (R = SiMe3 and Ph)
Nanjo, Masato,Oda, Takashi,Mochida, Kunio
, p. 100 - 108 (2007/10/03)
The trimethylsilyl-substituted germylzinc halides, (Me3Si) 3GeZnX (X = Cl, Br, and I), and silylzinc chlorides, R(Me3Si)2SiZnCl (R = SiMe3 and Ph) have been prepared and their molecular structures have been full determined by spectroscopic and single-crystal X-ray diffraction methods. The germylzinc halides and silylzinc chlorides have dimeric structures consisting of two μ-halogen atoms. The reactivity of germylzinc chloride with substrates is also examined.
