Abstract
Catalytic reactions resulting from our C-X (X = H, C, O, N, halide) bond activation studies are described. Aryl chlorides can react with aluminum alkyls in preference to bromides. Using PCP-type Pd catalysts, Heck reaction with aryl iodides and bromides can proceed without involvement of Pd(0). Ru-catalyzed oxidative coupling of arenes with alkenes using O2 was accomplished. Using specifically designed systems, the scope and mechanisms of C-C activation in solution was studied and compared to C-H activation. C-C activation by Rh(I), Ir(I), Ni(II), Pt(II), Ru(II), and Os(II) was observed. Metal insertion into a strong C-C bond can be kinetically and thermodynamically more favorable than the competing C-H activation. Selective, single-step oxidative addition of a strong C-C bond to a metal was observed and kinetically evaluated. Catalytic C-C hydrogenolysis was demonstrated. A combination of C-C activation and C-R formation (R = aryl, silyl) resulted in unusual methylene transfer chemistry. Selective activation of aryl-O and Me-O bonds was observed. New types of interactions between metals and arenes and unusual quinonoid complexes, including quinone methides, xylylenes, methylene arenium, and a metallaquinone, were discovered. C-H and C-C agostic complexes of cationic metals, proposed as intermediates in bond activation, were isolated. Stabilization and controlled release of biologically relevant, extremely unstable, simple quinone methides, was accomplished.
| Original language | English |
|---|---|
| Pages (from-to) | 445-460 |
| Number of pages | 16 |
| Journal | Pure and Applied Chemistry |
| Volume | 75 |
| Issue number | 4 |
| Publication status | Published - Apr 1 2003 |
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Challenging metal-based transformations. From single-bond activation to catalysis and metallaquinonoids. / Milstein, David.
In: Pure and Applied Chemistry, Vol. 75, No. 4, 01.04.2003, p. 445-460.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Challenging metal-based transformations. From single-bond activation to catalysis and metallaquinonoids
AU - Milstein, David
PY - 2003/4/1
Y1 - 2003/4/1
N2 - Catalytic reactions resulting from our C-X (X = H, C, O, N, halide) bond activation studies are described. Aryl chlorides can react with aluminum alkyls in preference to bromides. Using PCP-type Pd catalysts, Heck reaction with aryl iodides and bromides can proceed without involvement of Pd(0). Ru-catalyzed oxidative coupling of arenes with alkenes using O2 was accomplished. Using specifically designed systems, the scope and mechanisms of C-C activation in solution was studied and compared to C-H activation. C-C activation by Rh(I), Ir(I), Ni(II), Pt(II), Ru(II), and Os(II) was observed. Metal insertion into a strong C-C bond can be kinetically and thermodynamically more favorable than the competing C-H activation. Selective, single-step oxidative addition of a strong C-C bond to a metal was observed and kinetically evaluated. Catalytic C-C hydrogenolysis was demonstrated. A combination of C-C activation and C-R formation (R = aryl, silyl) resulted in unusual methylene transfer chemistry. Selective activation of aryl-O and Me-O bonds was observed. New types of interactions between metals and arenes and unusual quinonoid complexes, including quinone methides, xylylenes, methylene arenium, and a metallaquinone, were discovered. C-H and C-C agostic complexes of cationic metals, proposed as intermediates in bond activation, were isolated. Stabilization and controlled release of biologically relevant, extremely unstable, simple quinone methides, was accomplished.
AB - Catalytic reactions resulting from our C-X (X = H, C, O, N, halide) bond activation studies are described. Aryl chlorides can react with aluminum alkyls in preference to bromides. Using PCP-type Pd catalysts, Heck reaction with aryl iodides and bromides can proceed without involvement of Pd(0). Ru-catalyzed oxidative coupling of arenes with alkenes using O2 was accomplished. Using specifically designed systems, the scope and mechanisms of C-C activation in solution was studied and compared to C-H activation. C-C activation by Rh(I), Ir(I), Ni(II), Pt(II), Ru(II), and Os(II) was observed. Metal insertion into a strong C-C bond can be kinetically and thermodynamically more favorable than the competing C-H activation. Selective, single-step oxidative addition of a strong C-C bond to a metal was observed and kinetically evaluated. Catalytic C-C hydrogenolysis was demonstrated. A combination of C-C activation and C-R formation (R = aryl, silyl) resulted in unusual methylene transfer chemistry. Selective activation of aryl-O and Me-O bonds was observed. New types of interactions between metals and arenes and unusual quinonoid complexes, including quinone methides, xylylenes, methylene arenium, and a metallaquinone, were discovered. C-H and C-C agostic complexes of cationic metals, proposed as intermediates in bond activation, were isolated. Stabilization and controlled release of biologically relevant, extremely unstable, simple quinone methides, was accomplished.
UR - http://www.scopus.com/inward/record.url?scp=0038782916&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=0038782916&partnerID=8YFLogxK
M3 - Article
AN - SCOPUS:0038782916
VL - 75
SP - 445
EP - 460
JO - Pure and Applied Chemistry
JF - Pure and Applied Chemistry
SN - 0033-4545
IS - 4
ER -