Synthesis 2021; 53(24): 4678-4681
DOI: 10.1055/a-1558-9135
paper

HMPA-Free Generation of Trialkylsilyllithium Reagents and Its Applications to the Synthesis of Silylboronic Esters

a   Graduate School of Advanced Science and Engineering, Hiroshima University, Higashi-Hiroshima 739-8526, Japan
b   Institut für Chemie, Technische Universität Berlin, Strasse des 17. Juni 115, 10623 Berlin, Germany
,
a   Graduate School of Advanced Science and Engineering, Hiroshima University, Higashi-Hiroshima 739-8526, Japan
,
a   Graduate School of Advanced Science and Engineering, Hiroshima University, Higashi-Hiroshima 739-8526, Japan
,
b   Institut für Chemie, Technische Universität Berlin, Strasse des 17. Juni 115, 10623 Berlin, Germany
,
a   Graduate School of Advanced Science and Engineering, Hiroshima University, Higashi-Hiroshima 739-8526, Japan
› Author Affiliations
JSPS fellowship for young scientists, JSPS KAKENHI Grant Number JP20J14589.


Abstract

Trialkylsilyllithium species have turned out to be facilely generated by treating hexaalkyldisilanes with methyllithium in the presence of tris(N,N-tetramethylene)phosphoric triamide (TPPA) as an activator, which can be trapped by boron electrophiles to afford silylboronic esters including long-awaited Me3Si–B(pin).

Supporting Information



Publication History

Received: 08 July 2021

Accepted after revision: 26 July 2021

Accepted Manuscript online:
26 July 2021

Article published online:
23 August 2021

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  • References


    • For reviews on the chemistry of silylboronic esters, see:
    • 1a Ohmura T, Suginome M. Bull. Chem. Soc. Jpn. 2009; 82: 29
    • 1b Oestreich M, Hartmann E, Mewald M. Chem. Rev. 2013; 113: 402
    • 1c Feng J.-J, Mao W, Zhang L, Oestreich M. Chem. Soc. Rev. 2021; 50: 2010
    • 2a Suginome M, Matsuda T, Ito Y. Organometallics 2000; 19: 4647
    • 2b Ohmura T, Masuda K, Furukawa H, Suginome M. Organometallics 2007; 26: 1291
  • 3 Tamao K, Kawachi A. Adv. Organomet. Chem. 1995; 38: 1

    • For transition-metal-catalyzed Si–H borylation of silanes, see:
    • 4a Boebel TA, Hartwig JF. Organometallics 2008; 27: 6013
    • 4b Shishido R, Uesugi M, Takahashi R, Mita T, Ishiyama T, Kubota K, Ito H. J. Am. Chem. Soc. 2020; 142: 14125

      For Me3Si–SiMe3, see:
    • 5a Still WC. J. Org. Chem. 1976; 41: 3063
    • 5b Hudrlik PF, Hudrlik AM, Yimenu T, Waugh MA, Nagendrappa G. Tetrahedron 1988; 44: 3791

    • For other Si–Si bond cleavage reactions, see:
    • 5c Gilman H, Holmes JM, Smith CL. Chem. Ind. 1965; 848
    • 5d Nicholson BK, Simpson J. J. Organomet. Chem. 1974; 72: 211
    • 5e Gilman H, Smith CL. J. Organomet. Chem. 1968; 14: 91
    • 5f Gutekunst G, Brook AG. J. Organomet. Chem. 1982; 225: 1

      For biological effects of HMPA, see:
    • 6a Jackson H, Jones A, Cooper E. J. Reprod. Fert. 1969; 20: 263
    • 6b Jones A, Jackson H. Biochem. Pharmacol. 1970; 19: 603
    • 6c Kimbrough R, Gaines T. Bull. Environ. Contam. Toxicol. 1973; 10: 225
    • 6d Zapp JA. Jr. Am. Ind. Hyg. Assoc. J. 1975; 36: 916
    • 6e Lee KP, Trochimowicz HJ. J. Natl. Cancer Inst. 1982; 68: 157
    • 6f Mihal CP. Jr. Am. Ind. Hyg. Assoc. J. 1987; 48: 997
    • 6g Aguirrezabalaga I, Nivard M, Comendador M, Vogel E. Genetics 1995; 139: 649
  • 7 Carcinogenicity of HMPA is due to hydroxylation at N-methyl groups by cytochrome P450 enzymes with concomitant release of formaldehyde within the nasopharyngeal cells; see ref 6b. Besides, hexaethylphosphoric triamide (HEPA) is reported to be non-carcinogenic; see ref. 8c and Zilstra, J. A.; Proefschrift; Rijks-Universiteit Leiden: The Netherlands, 1987, and references cited therein. Moreover, higher boiling point of TPPA could also contribute to the lower toxicity, as is the case with diHMPA, see ref 8a.

    • A small number of reactions employing HMPA surrogates have been reported, see:
    • 8a McDonald CE, Ramsey JD, Grant JA, Howerter KA. Tetrahedron Lett. 2009; 50: 5308
    • 8b McDonald CE, Ramsey JD, Sampsell DG, Butler JA, Cecchini MR. Org. Lett. 2010; 12: 5178
    • 8c Berndt M, Hölemann A, Niermann A, Bentz C, Zimmer R, Reissig H.-U. Eur. J. Org. Chem. 2012; 1299
  • 9 Smith JG, Henke SL, Mohler EM, Morgan L, Rajan NI. Synth. Commun. 1991; 21: 1999
  • 10 Use of LiBr-free MeLi was effective for the lithiation of Et3Si–SiEt3, see Supporting Information for details.
  • 11 CCDC 2086528 contains the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/structures.
  • 12 A prior version of the present article was deposited as a preprint on ChemRxiv, see: Kamio S, Imagawa T, Nakamoto M, Oestreich M, Yoshida H. ChemRxiv 2021; DOI: 10.26434/chemrxiv.14737362.v1.
  • 13 Heckel A, Seebach D. Chem. Eur. J. 2002; 8: 559