By Shinji Murai

Within the previous few years a wide repetoire of tools for the activation of unreactive natural functionalities and for his or her use in natural synthesis has been constructed. during this quantity, components starting from the activation of C-H bonds to the chemical transformation of dinitrogen are authoritatively mentioned by means of prime specialists within the box. To turn on potential in order to cleave differently inert chemical bonds. The cleavage and formation of chemical bonds is key to natural synthesis; those new activation methodologies make hitherto infeasible reactions tremendous effortless and create new possibilities for leading edge natural differences, for either and academia. this is often the 1st booklet that gives an intensive and well timed assurance of either inorganic and natural artificial features of bond activation, hence giving a extensive evaluation of the sector and permitting either inorganic and natural chemists prepared entry to the methodologies concerned.

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But But P But H H Ir P But (36) + But + 150 °C But 82 TON/min A similar iridium complex, [IrH2(acetone)2PPh3]SbF6 [73], catalyzes the selective dehydrogenation of cyclohexenes to arenes. In this case, the cyclohexenes work as the substrate and also as the hydrogen acceptor. Highly efficient transfer-dehydrogenation of alkanes was reported by Goldman [74–77], using a unique catalyst system. A high pressure (1000 psi) of hydrogen is used for the dehydrogenation reaction [75–77]. 2 M) (Eq. 37). The proposed mechanism for this paradoxical catalytic reaction involves the addition of H2, loss of CO, and transfer of H2 to a sacrificial acceptor, thereby generating RhCl(PMe3)2, which is the same catalytically active species proposed in the photochemical dehydrogenation of alkanes with RhCl(CO)(PMe3)2 (Scheme 2).

Intermolecular Hydroacylation of Olefins . . . . . . . . Hydroacylation of Acetylenes . . . . . . . . . . . 2 Michael Addition and Aldol Reactions . . . . . . . . . Addition to Carbon-Carbon Multiple Bonds . . . . . . . 72 73 6 Conclusion . . . . . . . . . . . . . . . . . 75 References . . . . . . . . . . . . . . . . . . . 76 Topics in Organometallic Chemistry, Vol. 3 Volume Editor: S. Murai © Springer-Verlag Berlin Heidelberg 1999 48 Fumitoshi Kakiuchi, Shinji Murai 1 Introduction One of the most valuable synthetic methods in organic synthesis is the direct use of otherwise unreactive C–H bonds with the aid of transition metal complexes.

5) [12]. This reaction is formally a dehydrogenative coupling. NH2 + H N Et RhCl3-3 H2O PPh3, 200 °C 100 kg/cm2 N + 30 TON (3) 10 TON TON = turnover numbers Me2NH + CH3OCH2CH2OCH3 + W(NMe2)n decaline 160 °C, 14 h H Me N (4) 7 TON IrH5(PiPr3)2 50 °C, 24 h RO R = CH3OCH2CH2 12 TON 45% + + RO RO 44% 11% (5) Heteroatom directed ethylation of the benzene ring in phenol was catalyzed by ruthenium(II)-phosphite complex. The alkylation takes place at the position ortho to the hydroxyl group exclusively, and the corresponding 1:2 addition product is the major product (Eq.

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