A method for the regioselective arylboration of isoprene and its derivatives is presented. These reactions allow for the synthesis of useful building blocks from simple components. Through these ...studies, an unusual additive effect with DMAP has been uncovered that allows for altered reactivity and the formation of quaternary carbon centers. The utility of this method is demonstrated toward the formal synthesis of mesembrine.
A method for the catalytic enantioselective arylboration of alkenylarenes is disclosed. The reaction leads to the formation of 1,1‐diarylalkanes that also incorporate an additional pinacol boronic ...ester which can be easily transformed to a variety of groups. The products are formed with excellent diastereoselectivities and enantioselectivities.
Incorporate and transform: The title reaction yields 1,1‐diarylalkanes and simultaneously incorporates a pinacol boronic ester, which can be easily transformed to a variety of groups. Products are formed with excellent diastereoselectivities and enantioselectivities.
Cyclobutanes and cyclobutenes are important structural motifs found in numerous biologically significant molecules, and they are useful intermediates for chemical synthesis. Consequently, 2+2 ...cycloadditions to access cyclobutanes and cyclobutenes have been established to be particularly useful transformations. Within the last 10 years, an increase in the frequency of publications for catalytic enantioselective 2+2 cycloadditions has occurred. These reactions provide access to a wide array of enantiomerically enriched chemical diversity that was not previously attainable. Described in this review are the advances made in catalytic enantioselective 2+2 cycloadditions to access cyclobutanes and cyclobutenes.
Squared away: Cyclobutanes and cyclobutenes are important structural motifs found in numerous biologically significant molecules, and they are useful intermediates for chemical synthesis. Consequently, catalytic enantioselective 2+2 cycloadditions to access cyclobutanes and cyclobutenes have emerged as an attractive target for method development. The advances made in catalytic enantioselective 2+2 cycloadditions are described herein.
A method for the diastereoselective carboboration of 1,2‐disubstituted styrenes with aryl/vinyl bromides and (Bpin)2 is reported. High diastereoselectivities and yields are observed for the formation ...of either diastereomer of the product from a single alkene isomer. These reactions provide access to a diverse range of structures from simple starting materials.
The diastereoselective carboboration of 1,2‐disubstituted styrenes with aryl/vinyl bromides and (Bpin)2 proceeds with high diastereoselectivities and yields. The formation of either diastereomer of the product from a single alkene isomer is determined by the reaction conditions. The method thus provides access to a diverse range of structures from simple starting materials.
A method for the catalytic enantioselective diarylation of alkenes is presented. The method allowed for the synthesis of highly enantioenriched 2,3-dihydrobenzofurans and indolines containing ...molecules from readily available substrates. Furthermore, this method allowed for the enantioselective synthesis of quaternary carbons. Based on mechanism studies, the process likely functions by enantioselective insertion of an alkene into an Ar–CuBenzP* complex to generate a Csp3–Cu complex. Capture of this intermediate with an ArX led to formation of the desired product.
A method for the copper‐catalyzed borylacylation of activated alkenes is presented. The reaction involves borylcupration of the alkene, followed by capture of the generated alkyl–copper intermediate ...with an acid chloride. The reactions operated with low catalyst loading and generally occurre within 15 min at room temperature for a range of activated alkenes. In the case of vinyl arenes, enantioselective borylacylation was possible.
Give 'em the new one, two: A range of activated alkenes underwent rapid copper‐catalyzed borylacylation at room temperature at low catalyst loadings (see scheme). The reaction involves borylcupration of the alkene and capture of the resulting alkyl–copper intermediate with an acid chloride. In the case of vinyl arenes, the transformation could be carried out in an enantioselective manner.
A synergistic Pd/Cu system for the coupling of alkenes, (Bpin)2 (pin=pinacolate), and aryl/vinyl bromides is disclosed. This method allows for the catalytic generation of secondary Csp3Cu ...nucleophiles in situ and subsequent Pd‐catalyzed cross‐coupling.
A synergistic Pd/Cu system for the coupling of alkenes, (Bpin)2 (pin=pinacolate), and aryl/vinyl bromides, was disclosed. This method allowed the catalytic generation of secondary Csp3Cu nucleophiles in situ and subsequent Pd‐catalyzed cross‐coupling. The products generated from these reactions are easily amenable to functionalization and are closely related to several families of biologically relevant molecules (see scheme).
Copper‐catalyzed Suzuki–Miyaura‐type cross‐coupling and carboboration processes are reported. The cross‐couplings function well with a variety of substituted aryl iodides and aryl boronic esters and ...allows for orthogonal reactivity compared to palladium‐catalyzed processes. The carboboration method includes both alkynes and allenes and provides access to highly substituted and stereodefined vinyl boronic esters. The alkyne carboboration method is highlighted in the simple one‐pot synthesis of Tamoxifen.
Cross‐Cu‐pling: The title cross‐couplings function well with a variety of substituted aryl iodides and aryl boronic esters and allows for reactivity orthogonal to that of the palladium‐catalyzed processes. The title carboboration method includes both alkynes and allenes and provides access to highly substituted and stereodefined vinyl boronic esters. The alkyne carboboration method is highlighted in a simple one‐pot synthesis of Tamoxifen.
A method for the Ni-catalyzed arylboration of unactivated monosubstituted, 1,1-disubstituted, and trisubstituted alkenes is disclosed. The reaction is notable in that it converts highly substituted ...alkenes, aryl bromides, and diboron reagents to products that contain a quaternary carbon and a synthetically versatile carbon–boron bond with control of stereoselectivity and regioselectivity. In addition, the method is demonstrated to be useful for the synthesis of saturated nitrogen heterocycles, which are important motifs in pharmaceutical compounds. Finally, due to the unusual reactivity demonstrated, the mechanistic details of the reaction were studied with both computational and experimental techniques.
A method for the regiodivergent arylboration of dienes is presented. These reactions allow for the formation of a diverse range of synthetically versatile products from simple precursors. Through ...mechanistic studies, these reactions likely operate by initial addition of a Cu–Bpin complex across the diene followed by Pd-catalyzed cross coupling with an aryl halide or pseudohalide.
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