875094-24-9Relevant academic research and scientific papers
Ruthenium-catalyzed homo and cross metathesis reactions of alkenylpolyboranes: New routes to functional o-carborane and decaborane derivatives
Wei, Xiaolan,Carroll, Patrick J.,Sneddon, Larry G.
, p. 609 - 621 (2008/10/09)
Both 1-(CH2=CHCH2)-1,2-C2B 10H11 (1) and 6-[CH2=CH(CH2) 4]-B10H13 (2) undergo homometathesis and cross metathesis reactions in the presence of the Cl2Ru(=CHPh)(PCy 3)L, L = PCy3 (I) or H2IMes (II), Grubbs catalysts. According to the Grubbs classification, 1 is a type-II olefin for I and a type-I olefin for II and 2 is a type-I olefin for both the I and II catalysts. Homometathesis of 1 produces the olefin-bridged compound 1,1′-(CH2CH=CHCH2)-(1,2-C2B 10H11)2 (3), while the cross metathesis reactions of 1 with a variety of olefins are efficient, high-yield routes to functional o-carborane 1-R-1,2-C2B10H11 derivatives, including R = C6H5CH2CH=CHCH 2- (4), C6H5CH=CHCH2- (5), CH 3C(O)OCH2CH= CHCH2- (6), HOCH 2CH=CHCH2- (7), ClCH2CH=CHCH2- (8), C6H5CH2OCH2CH=CHCH2- (9), CH3(CH2)3CH=CHCH2- (10), CF 3C(O)OCH2CH=CHCH2- (11), CH3C(O) (CH2)2CH=CHCH2- (12), t-C4H 9OC(O)NHCH2CH=CHCH2- (13), NC(CH 2)3CH=CHCH2- (14), and {[(CH3) 4C2O2]BCH2CH= CHCH2}- (15). Deboronation of 1,1′-(CH2CH=CHCH2)-(1,2-C 2B10H11)2 (3) with CsF affords the olefin-bridged bis(dicarbollide) salt 2Cs+·[7,7′- (CH2CH=CHCH2)-7,8-(C2B9H 11)2]2- (16). Similar reactions of 1-[CH 3(CH2)3CH=CHCH2]-1,2-C 2B10H11 (10) with CsF and tetrabutylammonium fluoride generate the Cs+ (17) and [N(C4H 9)4]+ (18) [7-CH3(CH 2)3CH=CHCH2-7,8-C2B 9H11]- salts, respectively. Homometathesis of 2 affords 6,6′-[(CH2)4CH=CH(CH2) 4]-(B10H13)2 (19), and its cross metathesis reactions with functional olefins yield a range of functionalized decaborane derivatives 6-R-B10H13 (R = C6H 5CH2-CH=CH(CH2)4- (20), CH 3C(O)OCH2CH=CH(CH2)4- (21), C 6H5CH2OCH2CH==CH(CH 2)4- (22), ClCH2CH=CH(CH2) 4- (23), CH3(CH2)3CH=CH(CH 2)4- (24), CF3C(O)OCH2CH=CH(CH 2)4- (25), C6H5CH=CH(CH 2)4- (26), CH3C(O)(CH2) 2CH=CH(CH2)4- (27), CH3CH 2OCH2CH=CH(CH2)4- (28), and CH 3OC(O)CH=CH(CH2)4- (29)). Cross metathesis of 1 with 2 produces 1-[1-(1,2-C2B10H11)]-CH 2-CH=CH(CH2)4-7-(6-B10H 13) (30), having o-carborane and decaborane cages linked by an alkenyl bridge.
