TY - JOUR
T1 - Tandem Hydrosilylation/o-C-H Silylation of Arylalkynes Catalyzed by Ruthenium Bis(silyl) Aminophosphine Complexes
AU - Kitano, Takeo
AU - Komuro, Takashi
AU - Ono, Rikima
AU - Tobita, Hiromi
N1 - Funding Information:
This work was supported by JSPS KAKENHI Grant Numbers JP25410058 JP15H03782, and JP16K05714 from the Japan Society for the Promotion of Science (JSPS).
Publisher Copyright:
© 2017 American Chemical Society.
PY - 2017/8/14
Y1 - 2017/8/14
N2 - An unprecedented reaction via consecutive trans-selective hydrosilylation and o-C-H silylation of arylalkynes with hydrosilanes was developed by use of ruthenium complex catalysts Ru{ΰ3(Si,O,Si)-xantsil}(CO)(PR3) (R = NC4H8 (1-Pyrr), NC5H10 (1-Pip); xantsil = (9,9-dimethylxanthene-4,5-diyl)bis(dimethylsilyl)). This reaction proceeded with gentle heating at 40-60 °C and afforded novel 2,α-bis-silylated (Z)-stilbene or (Z)-styrene derivatives 2 together with an equimolar amount of (E)-/(Z)-arylalkenes as byproducts. The selectivity of the formation of 2 reached a maximum by employing catalyst 1-Pyrr ligated by the less bulky triaminophosphine P(NC4H8)3 and hydrosilane HSiMe(OSiMe3)2 having moderately bulky and electron withdrawing substituents.
AB - An unprecedented reaction via consecutive trans-selective hydrosilylation and o-C-H silylation of arylalkynes with hydrosilanes was developed by use of ruthenium complex catalysts Ru{ΰ3(Si,O,Si)-xantsil}(CO)(PR3) (R = NC4H8 (1-Pyrr), NC5H10 (1-Pip); xantsil = (9,9-dimethylxanthene-4,5-diyl)bis(dimethylsilyl)). This reaction proceeded with gentle heating at 40-60 °C and afforded novel 2,α-bis-silylated (Z)-stilbene or (Z)-styrene derivatives 2 together with an equimolar amount of (E)-/(Z)-arylalkenes as byproducts. The selectivity of the formation of 2 reached a maximum by employing catalyst 1-Pyrr ligated by the less bulky triaminophosphine P(NC4H8)3 and hydrosilane HSiMe(OSiMe3)2 having moderately bulky and electron withdrawing substituents.
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U2 - 10.1021/acs.organomet.7b00528
DO - 10.1021/acs.organomet.7b00528
M3 - Article
AN - SCOPUS:85027396253
SN - 0276-7333
VL - 36
SP - 2710
EP - 2713
JO - Organometallics
JF - Organometallics
IS - 15
ER -