Suzuki mechanism

One difference between the Suzuki mechanism and that of the Stille Coupling is that the boronic acid must be activated, for example with base. This activation of the boron atom enhances the polarisation of the organic ligand, and facilitates transmetallation. If starting materials are substituted with base labile groups (for example esters), powdered KF effects this activation while leaving base labile groups unaffected. 

Included in the diagram is the alternative mechanism proposed by Watanabe [45, 46] in which the products were identified as alcohols and carboxylic acids. This was subsequently proved in error and the Suzuki mechanism is now widely accepted for the degrdation of poly(vinyl alcohol) by the microbes evaluated in his work. 

Later, fireflv oxyluciferin was successfully synthesi2ed (403. 408) and has been isolated and identified in firefly lanterns (luciola cruaciata) after the lanterns were treated with pyridine and acetic anhydride to prevent decomposition (409). In 1972, Suzuki and Goto firmly established that oxyluciferin is involved in the bioluminescence of firefly lanterns and in the chemiluminescence of firefly luciferin (403. 410).. A. mechanism involving a four-membered ring cyclic peroxide has been proposed for the reaction (406. 411). However, it was not confirmed by 0 -labelinE experiments (412). 

The mechanism " of the Suzuki reaction is closely related to that of the Stille coupling reaction, and is also best described by a catalytic cycle ... 

From Fig.2 (a), A solid phase transformation fiom hematite, Fc203 to magnetite, Fe304, is observed, indicating that the active sites of the catalj are related to Fc304. Suzuki et. al also found that Fe304 plays an important role in the formation of active centers by a redox mechanism [6]. It is also observed that the hematite itself relates to the formation of benzene at the initial periods, but no obvious iron carbide peaks are found on the tested Li-Fe/CNF, formation of which is considered as one of the itsisons for catalyst deactivation [3,6]. 

KOBAYASHI Y, SUZUKI M, SATSU H, ARAI S, KARA Y, SUZUKI K, MIYAMOTO Y, SHIMIZU M (2000) Green tea polyphenols inhibit the sodiiun-dependent glucose transporter of intestinal epithelial cells by a competitive mechanism. JAgric Food Chem. 48 5618-23. 

This reaction typifies the two possibilities of reaction routes for M-catalyzed addition of an S-X (or Se-X) bond to alkyne (a) oxidative addition of the S-X bond to M(0) to form 94, (b) insertion of alkyne into either the M-S or M-X bond to provide 95 or 96 (c) C-X or C-S bond-forming reductive elimination to give 97 (Scheme 7-21). Comparable reaction sequences are also discussed when the Chalk-Harrod mechanism is compared with the modified Chalk-Harrod mechanism in hydrosily-lations [1,3]. The palladium-catalyzed thioboratiori, that is, addition of an S-B bond to an alkyne was reported by Miyaura and Suzuki et al. to furnish the cis-adducts 98 with the sulfur bound to the internal carbon and the boron center to the terminal carbon (Eq. 7.61) [62]. 

Suematsu, M., Suzuki, M., Miura, S., Miura, S., Suzuki, K., Hibi, T., Watanabe, M. and Tsuchiya (1987b). Sulfasalazine and its metabolites attenuate respiratory burst of leukocytes -a possible mechanism of anti-inflammatory effects. J. Clin. Lab. Immunol. 23, 31-33. 

Scheme 27.1. Proposed mechanism for Suzuki coupling by Pd-doped perovskite catalysts.

Chiba K, Hoshino Y, Suzuki C, et al. FTY720, a novel immunosuppressant possessing unique mechanisms. I. Prolongation of skin allograft survival and synergistic effect in combination with cyclosporine in rats. Transplant Proc 1996 28(2) 1056-1059. 

Figure 10.3 (a) Proposed mechanism for induction of NFKB proteins (from Suzuki et al., 1994) (b) interaction with iron metabolism. Reproduced with permission from Cairo and Pietrangelo, 2000, the Biochemical Society. 

Mizoguchi, H., Tseng, L. F., Suzuki, T., Sora, I. and Narita, M. Recent advances in the search for the p-opioidergic system differential mechanism of g-protein activation induced by endogenous p-opioid peptides, endomorphin and 5-endorphin. Jpn. J. Pharmacol. 89 239-244, 2002. 

Brown and Suzuki have shown that treatment of trialkylboranes with ethenyl-(Scheme 42, Eq. 42a) and ethynyloxiranes (Scheme 42, Eq. 42b) in the presence of a catalytic amount of oxygen, affords the corresponding allylic or allenic alcohols. The mechanism may involve the addition of alkyl radicals to the unsaturated system leading to l-(oxiranyl)alkyl and l-(oxiranyl)alkenyl radicals followed by rapid fragmentation to give alkoxyl radicals that finally complete the chain process by reacting with the trialkylborane [104-106]. 

Thermal (electrophilic) and photochemical (charge-transfer) nitrations share in common the rapid, preequilibrium formation of the EDA complex [ArH, PyNO ]. Therefore let us consider how charge-transfer activation, as established by the kinetic behaviour of the reactive triad in Scheme 12, relates to a common mechanism for electrophilic nitration. Since the reactive intermediates pertinent to the thermal (electrophilic) process, unlike those in its photochemical counterpart, cannot be observed directly, we must rely initially on the unusual array of nonconventional nitration products (Hartshorn, 1974 Suzuki, 1977) and the unique isomeric distributions as follows. 

In comparison with the hydroboration and diborafion reactions, thioboration reactions are relatively limited. In 1993, Suzuki and co-workers reported the Pd(0)-catalyzed addition of 9-(alkylthio)-9-BBN (BBN = borabicyclo [3.3.1] nonane) derivatives to terminal alkynes to produce (alkylthio)boranes, which are known as versatile reagents to introduce alkylthio groups into organic molecules [21], Experimental results indicate that the thioboration reactions, specific to terminal alkynes, are preferentially catalyzed by Pd(0) complexes, e.g. Pd(PPh3)4, producing (thioboryl)alkene products, in which the Z-isomers are dominant. A mechanism proposed by Suzuki and co-workers for the reactions involves an oxidative addition of the B-S bond to the Pd(0) complex, the insertion of an alkyne into the Pd-B or Pd-S bond, and the reductive elimination of the (thioboryl)alkene product. 

The dynamic viscoelastic properties of acetylated wood have been determined and compared with other wood treatments in a number of studies. Both the specific dynamic Young s modulus (E /j) and tan S are lower in acetylated wood compared with unmodified wood (Akitsu etal., 1991, 1992, 1993a,b Korai and Suzuki, 1995 Chang etal., 2000). Acetylation also reduces mechanosorptive creep deformation of the modified wood (Norimoto etal., 1992 Yano etal, 1993). In a study of the dynamic mechanical properties of acetylated wood under conditions of varying humidity, it was concluded that the rate of diffusion of moisture into the wood samples was not affected by acetylation (Ebrahimzadeh, 1998). 

Korai, H., Kiguchi, M., Hosoya, S., Suzuki, S., Hirano, Y. and Iwata, R. (2001). Improvements of fiberboard made from acetylated fibers by ozonation I effect of ozonation on mechanical properties. Journal of Wood Science, 47(1), 24—29. 

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