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Reactivity of Phenylacetylene toward Unsymmetrical Disilenes: Regiodivergent [2+2] Cycloaddition vs. CH Addition
Author(s) -
Kell Andreas T.,
Obeid Naim M.,
Bag Prasenjit,
Zimmer Michael,
Huch Volker,
Scheschkewitz David
Publication year - 2021
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.202100137
Subject(s) - phenylacetylene , cycloaddition , chemistry , regioselectivity , reactivity (psychology) , substituent , deprotonation , photochemistry , medicinal chemistry , stereochemistry , catalysis , organic chemistry , medicine , ion , alternative medicine , pathology
We report the regiodivergent reaction of phenylacetylene with a selection of disilenes Tip 2 Si=SiTipR as well as bridged tetrasiladienes Tip 2 Si=SiTip−LU−SiTip=SiTip 2 (Tip=2,4,6‐ i Pr 3 C 6 H 2 , R=aryl groups; LU=arylene linkers). The regioselectivity of the [2+2] cycloaddition as determined by NMR spectroscopy and X‐ray crystallography is shown to strongly depend on the nature of the substituent R. The small size of the substituents compared to the Tip groups in both cases suggests a change in mechanism between the substrates with only hydrogen in the ortho ‐positions of R and LU and those with either ortho ‐methyl groups or condensed aromatic rings. In contrast, the presence of catalytic quantities of base completely suppresses cycloaddtion in favor of the formal CH addition of phenylacetylene. Quenching reactions with either MeI or MeOH after the stoichiometric application of deprotonated phenylacetylene as well as NMR studies at low temperature prove the intermediacy of an alkynyl‐substituted disilanyl lithium and thus suggest a carbolithiation pathway for the net CH addition.