- Asymmetric Synthesis of Silicon-Stereogenic Silanes by Copper-Catalyzed Desymmetrizing Protoboration of Vinylsilanes
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The catalytic asymmetric creation of silanes with silicon stereocenters is a long-sought but underdeveloped topic, and only a handful of examples have been reported. Moreover, the construction of chiral silanes containing (more than) two stereocenters is a more arduous task and remains unexploited. We herein report an unprecedented copper-catalyzed desymmetrizing protoboration of divinyl-substituted silanes with bis(pinacolato)diboron (B2pin2). This method enables the facile preparation of an array of enantiomerically enriched boronate-substituted organosilanes bearing contiguous silicon and carbon stereocenters with exclusive regioselectivity and generally excellent diastereo- and enantioselectivity.
- Li, Yanfei,Wang, Ying,Xiong, Tao,Zhang, Ge,Zhang, Qian
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supporting information
p. 11927 - 11931
(2020/05/22)
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- Entecavir intermediate and its preparation method
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The invention discloses an entecavir intermediate and a preparation method thereof. A provided preparation method for an entecavir intermediate compound 10 comprises the following steps: performing reducing reaction on an ester compound 11 in an organic solvent under the effect of a reducing agent, so as to obtain the compound 10. A provided preparation method for an entecavir intermediate compound 11 comprises the following steps: reacting a compound 12 with a hydroxyl protection reagent in an organic solvent in the presence of an acid to add a hydroxyl protection group, so as to obtain the compound 11. The preparation methods are cheap and easily available in raw materials, mild in reaction conditions, relatively high in product yield, good in atom economy, friendly to environment, and suitable for industrialized production.
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Paragraph 0380-0383; 0393; 0394; 0405
(2017/12/28)
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- Entecavir intermediate and its preparation method
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The invention discloses an entecavir intermediate and a preparation method thereof. A provided preparation method for an entecavir intermediate compound 8 comprises the following steps: performing hydroxyl protection group removal reaction on a compound 9 in a solvent under an acidic condition, so as to obtain the compound 8. A provided preparation method for an entecavir intermediate compound 9 comprises the following steps: performing hydroxyl protection group adding reaction on a compound 10 in an aprotic organic solvent under an alkali condition, so as to obtain the compound 9. The preparation methods are cheap and easily available in raw materials, mild in reaction conditions, relatively high in product yield, good in atom economy, friendly to environment, and suitable for industrialized production.
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Paragraph 0377-0382; 0391; 0392; 0402; 0405
(2017/12/28)
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- Cross-coupling of triallyl(aryl)silanes with aryl bromides and chlorides: An alternative convenient biaryl synthesis
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Cross-coupling of a diverse range of aryl bromides with triallyl(aryl)silanes is effective in the presence of PdCl2/PCy 3 and tetrabutylammonium fluoride (TBAF) in DMSO-H2O to give various biaryls in good yields. It is worthwhile to note that the all-carbon-substituted arylsilanes, stable towards moisture, acid, and base and easily accessible, serve as a highly practical alternative to their aryl(halo)silane counterparts. A catalyst system consisting of [η3-C3H5)PdCl]2 and 2-[2,4,6-(i-Pr)3C6Ha]-C6H4PCy 2 and use of TBAF· 3 H2O in THF-H2O are effective especially for the cross-coupling with aryl chlorides. Both of the catalyst systems tolerate a broad spectrum of common functional groups. The high efficiency of reactions is presumably due to the ready cleavage of the allyl groups upon treatment with TBAF·3 H2O and an appropriate amount of water. Diallyl(diphenyl)silane also cross-couples with various aryl bromides and chlorides in good yields, whereas allyl(triphenyl)silane gives the cross-coupled products in only moderate yields. Through sequential cross-coupling of bromochlorobenzenes with different arylsilanes, a range of unsymmetrical terphenyls are accessible in good overall yields.
- Sahoo, Akhila K.,Oda, Takuro,Nakao, Yoshiaki,Hiyama, Tamejiro
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p. 1715 - 1727
(2007/10/03)
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- Nickel-catalyzed cross-couplings of organosilicon reagents with unactivated secondary alkyl bromides
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A metal-catalyzed cross-coupling of organosilicon compounds with alkyl halides has been developed. Noteworthy attributes of the method are its scope (secondary electrophiles), its high functional-group compatibility, and the air stability of the catalyst components. Copyright
- Powell, David A.,Fu, Gregory C.
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p. 7788 - 7789
(2007/10/03)
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