347374-00-9Relevant academic research and scientific papers
Syntheses and reactions of a stable 1,2-dichloro-1,2-diborolane and aromatic tetraboranes
Praesang, Garsten,Sahin, Yueksel,Hofmann, Matthias,Geiseler, Gertraud,Massa, Werner,Berndt, Armin
, p. 3063 - 3073 (2004)
The 1,2-dichloro-1,2-diborolane 1b was isolated in good yield after the reaction of the 1,2-bis(dimethylamino)-1,2-diborolane 2c with BCl3. We prepared 2c from 1,2-bis(dimethylamino)-1,2-dichlorodiborane(4) (3) and TMEDA-free [1,3-bis(trimethylsilyl)allyl]lithium (5a·Li), which is accessible by deprotonation of 1,3-bis(trimethylsilyl)propene (4a) with n-butyllithium in diethyl ether. Upon its reaction with lithium in THF, the 1-allyl-2-chlorodiborane(4) 6a obtained in the first step undergoes an unprecedented ring closure with 1,2-migration of a trimethylsilyl substituent to yield the boron-stabilized carbanion 7a. Reaction of 7a with either chlorotrimethylsilane or HCl gives 2c or 2d, respectively. The latter compound cannot be transformed into an isolable 1,2-dichloro-1,2-diborolane; this observation demonstrates that a trimethylsilyl substituent next to each boron atom is essential for the stability of 1,2-dichloro-1,2-diborolanes. Compound 1b is a versatile starting material, inter alia for the syntheses of the aromatic tetraboranes(6) cis-11 and trans-13 and the aromatic tetraborane(4) cis-12. The isomerization cis-11 → trans-13 can be explained on the basis of reactions occurring under the conservation of two-electron aromaticity. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.
Synthesis and reactions of donor cyclopropanes: efficient routes to cis- and trans-tetrahydrofurans
Dunn, Jonathan,Dobbs, Adrian P.
supporting information, p. 7386 - 7414 (2015/08/24)
Abstract A detailed study on the synthesis and reactions of silylmethylcyclopropanes is reported. In their simplest form, these donor-only cyclopropanes undergo Lewis acid promoted reaction to give either cis- or trans-tetrahydrofurans, with the selectivity being reaction condition-dependant. The adducts themselves are demonstrated to be an important scaffold for structural diversification. The combination of a silyl-donor group in a donor-acceptor cyclopropane with novel acceptor groups is also discussed.
Silyl-cupration of a propargylsilane as a test for the reversibility of a metallo-metallation
De Dios, Maria Angeles Cubillo,Fleming, Ian,Friedhoff, Wibke,Woode, Philip D.W.
, p. 69 - 72 (2007/10/03)
Silyl-cupration of propargylsilanes is normal in giving mainly the product with a silyl group at the terminus and the copper atom in the centre. There is no evidence of the copper atom and the originally-resident silyl group undergoing a retro silyl-cupration to give an allenylsilane.
