Pt-Catalyzed Hydrosilylation of 1,3-Diynes with Triorganosilanes: Regio- and Stereoselective Synthesis of Mono- or Bis-silylated Adducts

Walkowiak, Jędrzej; Salamon, Katarzyna; Franczyk, Adrian; Stefanowska, Kinga; Szyling, Jakub; Kownacki, Ireneusz

doi:10.1021/acs.joc.8b03143

Cited by 40 publications

(21 citation statements)

References 43 publications

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“…After the reaction, boron moiety was presented at the internal position of the diyne system. The same regioselectivity was also observed for other hydrometallation processes, i. e. hydrosilylation, [28] hydrostannation [29] and hydromagnesiation. [30] In 2015, Yun et al reported the synthesis of borylsubstituted enynes via protoboration of symmetrical and unsymmetrical conjugated diynes with bis(pinacolato)diboron in methanol as a proton source.…”

Section: Introductionsupporting

confidence: 74%

Regio‐ and Stereoselective Synthesis of Enynyl Boronates via Ruthenium‐Catalyzed Hydroboration of 1,4‐Diaryl‐Substituted 1,3‐Diynes

et al. 2019

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A facile ruthenium‐catalyzed regio‐ and stereoselective hydroboration of symmetrical, aromatic 1,3‐diynes with pinacolborane towards 2‐boryl‐1,4‐diaryl‐buta‐1‐en‐3‐ynes and their further transformation into potassium trifluoroborate salts is presented. The reaction proceeded efficiently for 1,4‐diphenylbutadiynes with various substituents on the phenyl rings and heterocyclic 1,4‐di(thiophen‐3‐yl)buta‐1,3‐diyne. The resulting products were isolated and fully characterized (1H, 13C, 11B and 1D NOESY NMR, IR, GC‐MS, HRMS or elemental analysis). Moreover, the crystal structure of an enynyl boronate was determined, proving the addition of boryl moiety at the internal carbon in the diyne, according to the anti‐Markovnikov rule. The results presented here are the first examples of selective catalytic monohydroboration of conjugated diynes. The products obtained due to the presence of the boryl group and the unsaturated bonds are potential synthons in the synthesis of natural compounds or active pharmaceutical ingredients (API). The model Suzuki coupling of 2‐boryl‐1,4‐diphenyl‐buta‐1‐en‐3‐ynes with iodobenzene was carried out to illustrate the utility of the resulting compounds.

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Section: Introductionsupporting

confidence: 74%

Regio‐ and Stereoselective Synthesis of Enynyl Boronates via Ruthenium‐Catalyzed Hydroboration of 1,4‐Diaryl‐Substituted 1,3‐Diynes

et al. 2019

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“…On the basis of our previous experience [11] and literature reports regarding hydrosilylation of 1,4-disubstituted 1,3-butadiynes with silanes, [12] reactions of nine structurally and electronically different 1,3-diynes (2 a-i) (Scheme 1) with (HSiMe 2 O)(i-Bu) 7 Si 8 O 12 (1) were performed (in the presence of platinum catalysts: Pt 2 (dvs) 3 (Karsted's catalyst), Pt(PPh 3 ) 4 , PtO 2 and Pt/ SDB (SDB-styrene-divinylbenzene copolymer), [10b] in an air atmosphere, without any purification of the acquired chemicals). Processes were carried out at temperatures between 40°C and 100°C or at room temperature.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of Functional 3‐Buten‐1‐ynes and 1,3‐Butadienes with Silsesquioxane Moiety via Hydrosilylation of 1,3‐Diynes

et al. 2019

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Highly effective procedures for the addition of one or two molecules of 1-dimethylsiloxy-3,5,7,9,11,13,15-heptaisobutylpentacyclo-[9.5.1.1 3,9 .1 5,15 .1 7,13 ]octasiloxane ((HSiMe 2 O)(i-Bu) 7 Si 8 O 12 , (1)) to the symmetrically 1,4-disubstituted 1,3-diynes have been successfully developed for the first time. As a result, novel silsesquioxanes bearing substituents such as CH 3 , t-Bu, (CH 3 ) 2 OSi(CH 3 ) 3 , C 6 H 5 , C 6 H 4 Br-4, C 6 H 4 (BO 2 C 2 (CH 3 ) 4 )-4, OH, COOCH 3 , and morpholino were obtained and characterized by 1 H, 13 C, 29 Si NMR and mass spectrometry. Detailed optimization of reaction conditions was performed with a wide range of temperatures, in the presence of various types of catalysts and ratios of reagents, to obtain complex information about the process selectivity and develop efficient methods for synthesizing targeted compounds. It was found that precisely optimized approaches provided 3-buten-1-ynes or 1,3-butadienes with high yields, without decomposition of other reactive functionalities presented in the molecule structure. Due to the presence of reactive functional groups, the resulting compounds constituted a new silsesquioxane family characterized by unique structures and potential applications.

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“…Analogue influence of the t -Bu and (CH 3 ) 2 OSi(CH 3 ) 3 groups on forming the product of monohydrosilylation of 1,3-diynes was previously observed. 69 , 70 …”

Section: Resultsmentioning

confidence: 99%

Alkenyl-Functionalized Open-Cage Silsesquioxanes (RSiMe₂O)₃R′₇Si₇O₉: A Novel Class of Building Nanoblocks

et al. 2021

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Trifunctional incompletely condensed polyhedral oligomeric silsesquioxanes (RSiMe 2 O) 3 R′ 7 Si 7 O 9 ( IC-POSS s) are considered as intriguing building nanoblocks dedicated to constructing highly advanced organic–inorganic molecules and polymers. Up to now, they have been mainly obtained via hydrosilylation of olefins, while the hydrosilylation of the C≡C bonds has not been studied at all, despite the enormous potential of this approach resulting from the possibility of introducing 3, 6, or even more functional groups into the IC-POSS structure. Therefore, in this work, we present a highly selective and efficient synthesis of the first example of tripodal alkenyl-functionalized IC-POSS s, obtained via platinum-catalyzed hydrosilylation of the terminal and internal alkynes, as well as symmetrically and nonsymmetrically 1,4-disubstituted buta-1,3-diynes with silsesquioxanes (HSiMe 2 O) 3 R′ 7 Si 7 O 9 (R′ = i -C 4 H 9 ( 1a ), (H 3 C) 3 CH 2 C(H 3 C)HCH 2 C ( 1b )). The resulting products are synthetic intermediates that contain C=C bonds and functional groups (e.g., OSiMe 3 , SiR 3 , Br, F, B(O(C(CH 3 ) 2 ) 2 (Bpin)), thienyl), which make them suitable for application in the synthesis of novel, complex, hybrid materials with unique properties.

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Pt-Catalyzed Hydrosilylation of 1,3-Diynes with Triorganosilanes: Regio- and Stereoselective Synthesis of Mono- or Bis-silylated Adducts

Cited by 40 publications

References 43 publications

Regio‐ and Stereoselective Synthesis of Enynyl Boronates via Ruthenium‐Catalyzed Hydroboration of 1,4‐Diaryl‐Substituted 1,3‐Diynes

Regio‐ and Stereoselective Synthesis of Enynyl Boronates via Ruthenium‐Catalyzed Hydroboration of 1,4‐Diaryl‐Substituted 1,3‐Diynes

Synthesis of Functional 3‐Buten‐1‐ynes and 1,3‐Butadienes with Silsesquioxane Moiety via Hydrosilylation of 1,3‐Diynes

Alkenyl-Functionalized Open-Cage Silsesquioxanes (RSiMe₂O)₃R′₇Si₇O₉: A Novel Class of Building Nanoblocks

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Pt-Catalyzed Hydrosilylation of 1,3-Diynes with Triorganosilanes: Regio- and Stereoselective Synthesis of Mono- or Bis-silylated Adducts

Cited by 40 publications

References 43 publications

Regio‐ and Stereoselective Synthesis of Enynyl Boronates via Ruthenium‐Catalyzed Hydroboration of 1,4‐Diaryl‐Substituted 1,3‐Diynes

Regio‐ and Stereoselective Synthesis of Enynyl Boronates via Ruthenium‐Catalyzed Hydroboration of 1,4‐Diaryl‐Substituted 1,3‐Diynes

Synthesis of Functional 3‐Buten‐1‐ynes and 1,3‐Butadienes with Silsesquioxane Moiety via Hydrosilylation of 1,3‐Diynes

Alkenyl-Functionalized Open-Cage Silsesquioxanes (RSiMe2O)3R′7Si7O9: A Novel Class of Building Nanoblocks

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Alkenyl-Functionalized Open-Cage Silsesquioxanes (RSiMe₂O)₃R′₇Si₇O₉: A Novel Class of Building Nanoblocks