Synthesis of multi-substituted vinylsilanes via copper(<scp>i</scp>)-catalyzed hydrosilylation reactions of allenes and propiolate derivatives with silylboronates

Xu, Yun‐He; Wu, Liu-Hai; Wang, Jun; Loh, Teck‐Peng

doi:10.1039/c4cc01722f

Cited by 54 publications

(10 citation statements)

References 37 publications

(14 reference statements)

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“…Finally,apreliminary study illustrates that the threecomponent approach to functionalized homoallylic amines can be extended to the silylative cross-coupling of allenes and imines. [18] Employing Suginomes reagent, Me 2 PhSiBpin, [19] in arelated copper-catalyzed assembly involving 1a and 2a gave the homoallylic amine 3x with complete regiocontrol, high diastereocontrol, and in good yield (Scheme 8).…”

Section: Angewandte Chemiementioning

confidence: 99%

Copper‐Catalyzed Borylative Cross‐Coupling of Allenes and Imines: Selective Three‐Component Assembly of Branched Homoallyl Amines

et al. 2015

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A copper‐catalyzed three‐component coupling of allenes, bis(pinacolato)diboron, and imines allows regio‐, chemo‐, and diastereoselective assembly of branched α,β‐substituted‐γ‐boryl homoallylic amines, that is, products bearing versatile amino, alkenyl, and borane functionality. Alternatively, convenient oxidative workup allows access to α‐substituted‐β‐amino ketones. A computational study has been used to probe the stereochemical course of the cross‐coupling.

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Section: Angewandte Chemiementioning

confidence: 99%

Copper‐Catalyzed Borylative Cross‐Coupling of Allenes and Imines: Selective Three‐Component Assembly of Branched Homoallyl Amines

et al. 2015

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“…It was reported that Cu–Si species could react with allenes to form β‐silylated allylcopper intermediates 14. 15 Their three subsequent transformations were reported using different electrophiles: MeOH for hydrosilylation,14a,b aldehydes and ketones for 1,2‐addition,14a,c and CO 2 for silacarboxylation 15. Despite these advances, the challenging 1,4‐addition of β‐silylated allylcopper has never been uncovered, because efficient 1,2‐addtion remains favored versus 1,4‐addition in the addition of β‐functionalized allylcopper to α,β‐unsaturated carbonyls (Scheme ) 16.…”

Section: Methodsmentioning

confidence: 99%

Efficient Access to Bicyclo[4.3.0]nonanes: Copper‐Catalyzed Asymmetric Silylative Cyclization of Cyclohexadienone‐Tethered Allenes

Tang

Xie

et al. 2015

Angewandte Chemie

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The creation of three consecutive chiral carbon centers in one step is achieved using Cu-catalyzed asymmetric silylative cyclization of cyclohexadienone-tethered allenes. Through regioselective b-silylation of the allene and subsequent enantioselective 1,4-addition to cyclohexadienone,t his tandem reaction could afford cis-hydrobenzofuran, cis-hydroindole,a nd cis-hydroindene frameworks with excellent yields (80-98 %) and enantioselectivities (94-98 %ee) bearing vinylsilane and enone substructures.M eanwhile,t his mild transformation is generally compatible with aw ide range of functional groups,w hicha llows further conversion of the bicyclic products to bridged and tricyclic ring structures.

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“…These reactions tended to have high yields and high regioselectivity (Table ). Notably, two of these methods can be performed in water (Methods A and B) . Furthermore, Xu showed that silylation of an enynoate can proceed with exclusive addition to the β-carbon rather than the δ-carbon …”

Section: Silylations Using Silylboranesmentioning

confidence: 99%

Copper-Catalyzed Carbon–Silicon Bond Formation

et al. 2019

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Organosilanes have become a mainstay in organic synthesis as they can participate in a wide number of reactions where they act as a soft carbon nucleophile. They can engage in coupling reactions where C–C, C–N, C–O, or a variety of other bonds are formed. Furthermore, organosilanes are effective coupling partners in C–H activations. Despite their utility, synthesis of organosilanes typically relies on precious metals such as platinum and palladium. In the past several years, there has been considerable effort to develop new procedures, which rely on inexpensive catalysts such as first-row transition metals. More specifically, copper-catalyzed silylations have undergone significant development in the past decade. Copper-catalyzed silylations generally rely on either a silylborane, silylzinc, or disilane as the silicon source. However, a number of different transformations can be performed with this small set of reagents including conjugate addition, addition to alkynes, allenes, and carbonyls, coupling reactions, and substitutions. Nearly all of these transformations exhibit high levels of diastereoselectivity, regioselectivity, or enantioselectivity, depending on the transformation. Moreover, there is still plenty of room for further development of copper-catalyzed silylations, which should provide an inexpensive alternative to more traditional silylations.

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Synthesis of multi-substituted vinylsilanes via copper(i)-catalyzed hydrosilylation reactions of allenes and propiolate derivatives with silylboronates

Cited by 54 publications

References 37 publications

Copper‐Catalyzed Borylative Cross‐Coupling of Allenes and Imines: Selective Three‐Component Assembly of Branched Homoallyl Amines

Copper‐Catalyzed Borylative Cross‐Coupling of Allenes and Imines: Selective Three‐Component Assembly of Branched Homoallyl Amines

Efficient Access to Bicyclo[4.3.0]nonanes: Copper‐Catalyzed Asymmetric Silylative Cyclization of Cyclohexadienone‐Tethered Allenes

Copper-Catalyzed Carbon–Silicon Bond Formation

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