Reactivity of 1-allylsilatrane in ruthenium-catalyzed silylative coupling with olefins – mechanistic considerations

Bogna Sztorch 3 , Dawid Frąckowiak 2 , and Bogdan Marciniec 1 , 2
  • 1 Adam Mickiewicz University in Poznań, Faculty of Chemistry, Uniwersytetu Poznańskiego 8, 61-614, Poznań, Poland
  • 2 Center for Advanced Technology, Adam Mickiewicz University in Poznań, Uniwersytetu Poznańskiego 10, 61-614, Poznań, Poland
  • 3 Adam Mickiewicz University in Poznań, Center for Advanced Technology, Uniwersytetu Poznańskiego 10, 61-614, Poznań, Poland
Bogna Sztorch
  • Adam Mickiewicz University in Poznań, Center for Advanced Technology, Uniwersytetu Poznańskiego 10, 61-614, Poznań, Poland
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, Dawid Frąckowiak
  • Center for Advanced Technology, Adam Mickiewicz University in Poznań, Uniwersytetu Poznańskiego 10, 61-614, Poznań, Poland
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and Bogdan Marciniec
  • Corresponding author
  • Adam Mickiewicz University in Poznań, Faculty of Chemistry, Uniwersytetu Poznańskiego 8, 61-614, Poznań, Poland
  • Center for Advanced Technology, Adam Mickiewicz University in Poznań, Uniwersytetu Poznańskiego 10, 61-614, Poznań, Poland
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  • Search for other articles:
  • degruyter.comGoogle Scholar

Abstract

We have developed a new effective route for obtaining (E)-vinyl-substituted silatranes via ruthenium-catalyzed silylative coupling of 1-allylsilatrane with olefins. Experimental research allowed us also to propose the mechanism of the process based on stoichiometric reactions.

Introduction

Silatranes make a widely studied class of organosilicon compounds characterized by cage tricyclic structure, pentacoordinate silicon center with donor-acceptor transannular Si ← N bond, and interesting biological properties [1, 2, 3]. In the last three decades, research on silatranes covered several areas, including organic and organometallic synthesis [4, 5, 6], materials chemistry [7, 8, 9] as well as biochemistry and medicine [10, 11, 12, 13]

Given the variety of silatrane derivatives, allylsilatranes are hardly explored, which stands in stark contrast to the wide range of applications of allylsilanes in organic synthesis (e.g., in allylation of carbonyl compounds or olefin metathesis, for review see [14]). 1-Allylsilatrane (or allylsilatrane) 1 is the simplest representative of allyl-substituted silatranes (Figure 1).

Figure 1
Figure 1

Structure of 1-allylsilatrane.

Citation: Heterocyclic Communications 26, 1; 10.1515/hc-2020-0006

In literature, there are not many reports concerning the structural aspects of 1 and its reactivity. The crystal structure of 1 was determined in low temperature, and its correlation to hyperconjugation between the Si-C σ-electrons and the C=C π-system was discussed [15]. Allylsilatrane was functionalized in catalytic hydrosilylation and hydrogermylation, as well as in non-catalytic hydrostannation [16].

Platinum-catalyzed hydrosilylation of 1 was used in the preparation of oligosiloxanes with silatrane cages, which may find potential applications in lithium-ion conductive matrices [17]. There are also reports of reactivity of 1 toward electrophiles and nucleophiles [18,19] and dienes [20] (in Diels-Alder reactions).

In the last two decades, our group has developed a catalytic transformation involving vinylmetalloids and olefins, i.e., ruthenium-catalyzed trans-metalation, which leads to functionalized alkenyl-substituted boronates, silanes and germanes (Scheme 1) [21].

Scheme 1
Scheme 1

Ruthenium catalyzed trans-metalation of olefins with vinylmetalloids.

Citation: Heterocyclic Communications 26, 1; 10.1515/hc-2020-0006

In our previous study, we have reported the reactivity of vinylsilatrane in stereoselective trans-silylation with styrene derivatives catalyzed by RuHCl(CO)(PCy3)2, which leads to (E)-substituted alkenylsilatranes. We have also presented a detailed mechanism of this process, supported by studies and DFT calculations [22].

In this paper, we describe for the first time the reactivity of allylsilatrane in ruthenium-catalyzed transsilylation with olefins. Experimental examination, such as catalytic tests and stoichiometric reactions, allowed us to propose a mechanism for this transformation.

Results and discussion

Synthesis of allylsilatrane

Allylsilatrane 1 was prepared in the transesterification reaction of allyltrimethoxysilane with triethanolamine in boiling xylene in 82% yield, which is a slightly modified procedure based on the work of Corriu et al. [19] 1 Was isolated as white, powdery flakes stable in air and toward moisture.

Reactivity of allylsilatrane in trans-silylation with olefins

In 1999, Murai et al. presented an alternative protocol for the silylation of olefins by using allylsilanes as silylating agents [23]. The process was then dubbed as dehydrogenative silylation, even though it is a different variant of the silylative coupling reaction which proceeds with the evolution of propene instead of ethylene. The authors studied the reactions of allyltrimethyl- and allyltriethoxysilane with selected styrenes in the presence of RuHCl(CO) (PPh3)3 and isolated several (E)-triethoxystyrylsilanes.

We were able to use 1 as a silylating reagent for the catalytic synthesis of (E)-styrylsilatranes with selected styrenes in the presence of 2 mol% RuHCl(CO)(PCy3)2, which is the most efficient catalyst for the silylative coupling reaction (Table 1, Scheme 3).

Scheme 2
Scheme 2

Ruthenium-catalyzed silylation of olefins with triethoxyallylsilane.

Citation: Heterocyclic Communications 26, 1; 10.1515/hc-2020-0006

Scheme 3
Scheme 3

Trans-silylation of 1 with styrenes catalyzed by RuHCl(CO)(PCy3)2.

Citation: Heterocyclic Communications 26, 1; 10.1515/hc-2020-0006

Table 1

allylsilatrane 100 mg (0.46 mmol), olefin (1-3) 0.92 mmol, olefin (4) 0.46 mmol, 2 mol% RuHCl(CO)(PCy3)2, 110oC, toluene (3 mL), open system, 24 h

OlefinProductIsolated yield [%]
187
290
392
493

Examination of the 1H 13C 29Si NMR spectra, showed full conversion of 1 and confirmed that the reaction was (E)-selective. The same products could also be obtained when 1-vinylsilatrane acted as a silylating reagent, which was previously mentioned [22]. However, contrary to Murai’s report, the product of dimerization of 1 was not observed.

Nevertheless, the homocoupling of 1 catalyzed by 2 mol% of RuHCl(CO)(PCy3)2 gave 1-silatranyl-2-(silatranylmethyl)ethene in 90% yield as a mixture of E/Z isomers (Scheme 4).

Scheme 4
Scheme 4

Homocoupling of allylsilatrane.

Citation: Heterocyclic Communications 26, 1; 10.1515/hc-2020-0006

Mechanistic implications

The equimolar reaction of 1 with RuHCl(CO)(PCy3)2 in toluene-d8 carried out in a closed system (Young NMR tube) proved that the gas product of the reaction was propene (Scheme 5), which was confirmed by 1H NMR analysis. However, the 1H NMR spectrum also showed that the Ru–H proton signal did not entirely disappear, which was explained as a result of the regeneration of the complex during the initial stage of the catalytic cycle.

Scheme 5
Scheme 5

The equimolar reaction of 1 with RuHCl(CO)(PCy3)2.

Citation: Heterocyclic Communications 26, 1; 10.1515/hc-2020-0006

As the Ru-silatranyl complex is also the same intermediate in the coupling reaction of vinylsilatrane with olefins, we added styrene to the equimolar reaction system, which after 12 h was fully converted to (E)-styrylsilatrane 5 (Scheme 6).

Scheme 6
Scheme 6

The equimolar reaction of 1 with RuHCl(CO)(PCy3)2.

Citation: Heterocyclic Communications 26, 1; 10.1515/hc-2020-0006

Based on our experimental evidence and Murai’s work, as well as our previous study on silylative coupling of vinylsilatrane, we proposed a general mechanism for the first part of the catalytic cycle of ruthenium-catalyzed silylative coupling of 1 with olefins (Scheme 7).

Scheme 7
Scheme 7

Proposed mechanism for the first half of the catalytic cycle of silylative coupling of 1-allylsilatrane with olefins.

Citation: Heterocyclic Communications 26, 1; 10.1515/hc-2020-0006

Allylsilatrane 1 undergoes a 1,2-migratory insertion into the Ru–H bond of the ruthenium complex and forms intermediate A, which subsequently converts to more stable conformer B due to coordination of ruthenium center to the oxygen atom of silatrane framework. The ruthenium-silatranyl complex C is formed via β-elimination of propene molecule. The second part of the catalytic cycle is identical to the one present in coupling reaction of vinylsilatrane with olefins, which we previously mentioned [22].

Conclusions

We have developed catalytic trans-silylation of allylsilatrane with olefins leading to (E)-vinyl-substituted silatranes - the same products as those coming with vinylsilatrane as the substrate in very good yields. The mechanism for the coupling reaction of allylsilatrane with styrenes was studied by catalytic and stoichiometric reactions — the evolution of propene and formation of ruthenium-silatranyl species was confirmed. We also obtained a product of allylsilatrane homocoupling reaction — (E)-1-silatranyl-2-(silatranylmethyl)ethene.

Acknowledgements

The authors gratefully acknowledge the financial support from the National Science Centre (OPUS project UMO-2017/27/B/ST5/00149). This research was supported in part by PL-Grid Infrastructure.

Conflicts of interest

The authors declare no conflict of interest.

References

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    Verkade JG. Main group atranes: chemical and structural features. Coord Chem Rev. 1994;137:233–95.

    • Crossref
    • Export Citation
  • [2]

    Chuit C, Corriu RJ, Reye C, Young JC. Reactivity of penta- and hexacoordinate silicon compounds and their role as reaction intermediates. Chem Rev. 1993;93(4):1371–448.

    • Crossref
    • Export Citation
  • [3]

    Puri JK, Singh R, Chahal VK. Silatranes: a review on their synthesis, structure, reactivity and applications. Chem Soc Rev. 2011;40(3):1791–840.

    • Crossref
    • PubMed
    • Export Citation
  • [4]

    Varjosaari SE, Skrypai V, Suating P, Hurley JJ, Gilbert TM, Adler MJ. 1-Hydrosilatrane: A Locomotive for Efficient Ketone Reductions. Eur J Org Chem. 2017;2(2):229–232.

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    Skrypai V, Hurley JJ, Adler MJ. Silatrane as a Practical and Selective Reagent for the Reduction of Aryl Aldehydes to Benzylic Alcohols. Eur J Org Chem. 2016;2016(12): 2207–11.

    • Crossref
    • Export Citation
  • [6]

    Vaejosaari SE, Skrypai V, Suating P, Hurley JJ, De Lio AM, Gilbert TM, et al. Simple Metal‐Free Direct Reductive Amination Using Hydrosilatrane to Form Secondary and Tertiary Amines. Adv Synth Catal. 2017;359:1872–78.

    • Crossref
    • Export Citation
  • [7]

    El Haskouri J, Cabrera S, Caldes M, Guillem C, Latorre J, Beltran A, et al. Surfactant-Assisted Synthesis of the SBA-8 Mesoporous Silica by Using Nonrigid Commercial Alkyltrimethyl Ammonium Surfactants. Chem Mater. 2002;14:2637–43.

    • Crossref
    • Export Citation
  • [8]

    El Haskouri J, Cabrera S, Caldes M, Guillem C, Latorre J, Beltran A, et al. Atrane Precursors in the One-Pot Surfactant-Assisted Synthesis of High Zirconium Content Porous Silicas. Chem Mater. 2002;14(12):5015–22.

    • Crossref
    • Export Citation
  • [9]

    Thanabodeekij N, Sadthayanon S, Gulari S, Wongkasemjit S. Extremely high surface area of ordered mesoporous MCM-41 by atrane route. Mater Chem Phys. 2006;98(1):131–7.

    • Crossref
    • Export Citation
  • [10]

    Sculimbrene BR, Decanio RE, Peterson BW, Muntel EE, Fenlon EE. Silatranyl-nucleosides: transition state analogues for phosphoryl transfer reactions. Tetrahedron Lett. 2001;42(30):4979–82.

    • Crossref
    • Export Citation
  • [11]

    Chen L, Xie Q, Sun L, Wang H. Synthesis and characterization of 1-ferrocenecarboxysilatranes and crystal structures of FcC(CH3) CHCOOSi(OCH2CH2)3N and p-FcC6H4COOSi(OCH2CH2)3N. J Organomet Chem. 2003;678(1-2):90–4.

    • Crossref
    • Export Citation
  • [12]

    Guo P, Ye F, Hu L, Liu J, Zhou L, Huang K, et al. Faming Zhuanli Shenqing Gongkai Shuomingshu, 2007, 19, 44, 442; Z. Li, X. Song, H. Su, J. Chen. Heterocycl Commun. 2005; 11:475.

  • [13]

    Li Z, Song X, Su H, Chen J. Synthesis of 1-substituted benzoyl aminopropyl silatranes and their biological activities. Heterocycl Commun. 2005;11(6):475.

  • [14]

    Chabaud L, James P, Landais Y. Allylsilanes in Organic Synthesis− Recent Developments. Eur J Org Chem. 2004;2004(15):3173–99.

    • Crossref
    • Export Citation
  • [15]

    White JM, Jones S. Low-temperature structure of allyl silatrane. Acta Crystallogr. 1999;C55:962-3.

  • [16]

    Voronkov MG, Adamovich SN, Khudyakov NM, Yu Khramtsova S, Rakhlin VI, Mirskov RG. Hydrosilylation, hydrogermylation and hydrostannylation of 1-alkenylsilatranes. Bull Acad Sci USSR, Div Chem Sci. 1986;35(2):451–2.

    • Crossref
    • Export Citation
  • [17]

    Mizumo T, Nakashima M, Ohshita J. Oligosiloxanes with Silatrane Moieties for Use in Lithium-ion Conductive Matrices. Silicon. 2017;9(1):85–96.

    • Crossref
    • Export Citation
  • [18]

    Voronkov MG, Baryshok VP, Petukhov LP, Rakhlin VI, Mirskov RG, Pestunovich VA. 1-Halosilatranes. J Organomet Chem. 1988;358(1-3):39–55.

    • Crossref
    • Export Citation
  • [19]

    Cerveau G, Chuit C, Corriu RJ, Reye C. Reactivity of hypervalent species of silicon: cleavage of the allyl-silicon bond. J Organomet Chem. 1987;328(3):C17–20.

    • Crossref
    • Export Citation
  • [20]

    Voronkov MG, Adamovich SN, Rakhlin VI, Mirskov RG, Sigalov MV. 1-Alkenyl- and 1-alkadienylsilatranes in the diels-alder reaction. Bull Acad Sci USSR, Div Chem Sci. 1984;33(12):2558–60.

    • Crossref
    • Export Citation
  • [21]

    Marciniec B. Catalytic coupling of sp2- and sp-hybridized carbon-hydrogen bonds with vinylmetalloid compounds. Acc Chem Res. 2007 Oct;40(10):943–52.

    • Crossref
    • PubMed
    • Export Citation
  • [22]

    Sztorch B, Frąckowiak D, Pyziak J, Czapik A, Hoffmann M, Marciniec B. Highly selective synthesis of substituted (E)-alkenylsilatranes via catalytic trans-silylation and mechanistic implications. Dalton Trans. 2017 Apr;46(15):4975–81.

    • Crossref
    • Export Citation
  • [23]

    Kakiuchi F, Yamada A, Naoto C, Murai S. Silyl Group Transfer from Allylsilanes to Olefins Catalyzed by a Ruthenium(II) Complex. Organometallics 1999 Apr;18(10):2033–2036

    • Crossref
    • Export Citation

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  • [1]

    Verkade JG. Main group atranes: chemical and structural features. Coord Chem Rev. 1994;137:233–95.

    • Crossref
    • Export Citation
  • [2]

    Chuit C, Corriu RJ, Reye C, Young JC. Reactivity of penta- and hexacoordinate silicon compounds and their role as reaction intermediates. Chem Rev. 1993;93(4):1371–448.

    • Crossref
    • Export Citation
  • [3]

    Puri JK, Singh R, Chahal VK. Silatranes: a review on their synthesis, structure, reactivity and applications. Chem Soc Rev. 2011;40(3):1791–840.

    • Crossref
    • PubMed
    • Export Citation
  • [4]

    Varjosaari SE, Skrypai V, Suating P, Hurley JJ, Gilbert TM, Adler MJ. 1-Hydrosilatrane: A Locomotive for Efficient Ketone Reductions. Eur J Org Chem. 2017;2(2):229–232.

  • [5]

    Skrypai V, Hurley JJ, Adler MJ. Silatrane as a Practical and Selective Reagent for the Reduction of Aryl Aldehydes to Benzylic Alcohols. Eur J Org Chem. 2016;2016(12): 2207–11.

    • Crossref
    • Export Citation
  • [6]

    Vaejosaari SE, Skrypai V, Suating P, Hurley JJ, De Lio AM, Gilbert TM, et al. Simple Metal‐Free Direct Reductive Amination Using Hydrosilatrane to Form Secondary and Tertiary Amines. Adv Synth Catal. 2017;359:1872–78.

    • Crossref
    • Export Citation
  • [7]

    El Haskouri J, Cabrera S, Caldes M, Guillem C, Latorre J, Beltran A, et al. Surfactant-Assisted Synthesis of the SBA-8 Mesoporous Silica by Using Nonrigid Commercial Alkyltrimethyl Ammonium Surfactants. Chem Mater. 2002;14:2637–43.

    • Crossref
    • Export Citation
  • [8]

    El Haskouri J, Cabrera S, Caldes M, Guillem C, Latorre J, Beltran A, et al. Atrane Precursors in the One-Pot Surfactant-Assisted Synthesis of High Zirconium Content Porous Silicas. Chem Mater. 2002;14(12):5015–22.

    • Crossref
    • Export Citation
  • [9]

    Thanabodeekij N, Sadthayanon S, Gulari S, Wongkasemjit S. Extremely high surface area of ordered mesoporous MCM-41 by atrane route. Mater Chem Phys. 2006;98(1):131–7.

    • Crossref
    • Export Citation
  • [10]

    Sculimbrene BR, Decanio RE, Peterson BW, Muntel EE, Fenlon EE. Silatranyl-nucleosides: transition state analogues for phosphoryl transfer reactions. Tetrahedron Lett. 2001;42(30):4979–82.

    • Crossref
    • Export Citation
  • [11]

    Chen L, Xie Q, Sun L, Wang H. Synthesis and characterization of 1-ferrocenecarboxysilatranes and crystal structures of FcC(CH3) CHCOOSi(OCH2CH2)3N and p-FcC6H4COOSi(OCH2CH2)3N. J Organomet Chem. 2003;678(1-2):90–4.

    • Crossref
    • Export Citation
  • [12]

    Guo P, Ye F, Hu L, Liu J, Zhou L, Huang K, et al. Faming Zhuanli Shenqing Gongkai Shuomingshu, 2007, 19, 44, 442; Z. Li, X. Song, H. Su, J. Chen. Heterocycl Commun. 2005; 11:475.

  • [13]

    Li Z, Song X, Su H, Chen J. Synthesis of 1-substituted benzoyl aminopropyl silatranes and their biological activities. Heterocycl Commun. 2005;11(6):475.

  • [14]

    Chabaud L, James P, Landais Y. Allylsilanes in Organic Synthesis− Recent Developments. Eur J Org Chem. 2004;2004(15):3173–99.

    • Crossref
    • Export Citation
  • [15]

    White JM, Jones S. Low-temperature structure of allyl silatrane. Acta Crystallogr. 1999;C55:962-3.

  • [16]

    Voronkov MG, Adamovich SN, Khudyakov NM, Yu Khramtsova S, Rakhlin VI, Mirskov RG. Hydrosilylation, hydrogermylation and hydrostannylation of 1-alkenylsilatranes. Bull Acad Sci USSR, Div Chem Sci. 1986;35(2):451–2.

    • Crossref
    • Export Citation
  • [17]

    Mizumo T, Nakashima M, Ohshita J. Oligosiloxanes with Silatrane Moieties for Use in Lithium-ion Conductive Matrices. Silicon. 2017;9(1):85–96.

    • Crossref
    • Export Citation
  • [18]

    Voronkov MG, Baryshok VP, Petukhov LP, Rakhlin VI, Mirskov RG, Pestunovich VA. 1-Halosilatranes. J Organomet Chem. 1988;358(1-3):39–55.

    • Crossref
    • Export Citation
  • [19]

    Cerveau G, Chuit C, Corriu RJ, Reye C. Reactivity of hypervalent species of silicon: cleavage of the allyl-silicon bond. J Organomet Chem. 1987;328(3):C17–20.

    • Crossref
    • Export Citation
  • [20]

    Voronkov MG, Adamovich SN, Rakhlin VI, Mirskov RG, Sigalov MV. 1-Alkenyl- and 1-alkadienylsilatranes in the diels-alder reaction. Bull Acad Sci USSR, Div Chem Sci. 1984;33(12):2558–60.

    • Crossref
    • Export Citation
  • [21]

    Marciniec B. Catalytic coupling of sp2- and sp-hybridized carbon-hydrogen bonds with vinylmetalloid compounds. Acc Chem Res. 2007 Oct;40(10):943–52.

    • Crossref
    • PubMed
    • Export Citation
  • [22]

    Sztorch B, Frąckowiak D, Pyziak J, Czapik A, Hoffmann M, Marciniec B. Highly selective synthesis of substituted (E)-alkenylsilatranes via catalytic trans-silylation and mechanistic implications. Dalton Trans. 2017 Apr;46(15):4975–81.

    • Crossref
    • Export Citation
  • [23]

    Kakiuchi F, Yamada A, Naoto C, Murai S. Silyl Group Transfer from Allylsilanes to Olefins Catalyzed by a Ruthenium(II) Complex. Organometallics 1999 Apr;18(10):2033–2036

    • Crossref
    • Export Citation
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