Chalk-Harrod

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]. [Pg.242]

Hydrosilylation turned out to be a unique method in organosilicone chemistry, but in some cases it suffers from severe side reactions. An explanation is provided by the generally accepted reaction mechanism known as "Chalk-Harrod mechanism" described elsewhere [7]. Included in this series of reaction steps is an insertion of olefmic ligands into a platinum-hydrogen bond. Since the metal may be bonded to either of the unsaturated carbon atoms and the reaction is also an equilibrium, alkenes may result which are in fact isomerized starting material. Isomeric silanes are to be expected as well (Eq. 1), along with 1-hexylsilane, which is by far, the main compound produced. [Pg.254]

Wilkinson s catalyst brings about the hydrosilylation of a range of terminal alkenes (1-octene, trimethylvinylsilane) by 2-dimethylsilylpyridine with good regioselectivity for the anti-Markovnikoff product. Both 3-dimethylsilylpyridine and dimethylphenylsilane are less reactive sources of Si-H. In contrast, these two substrates are far more reactive than 2-dimethylsilylpyridine for the hydrosilylation of alkynes by [Pt(CH2 = CHSiMe2)20]/PR3 (R = Ph, Bu ). This difference was explained to be due to the operation of the two different pathways for Si-H addition—the standard Chalk-Harrod pathway with platinum and the modified Chalk-Harrod pathway with rhodium.108... [Pg.281]

Deuterium-labeling studies pointed to the operation of a nonstandard Chalk-Harrod mechanism for these reactions involving a silyl-alkene insertion step.133... [Pg.286]

Quickly, it became clear that iridium and rhodium do not cleanly fit the Chalk-Harrod mechanism as does platinum. For electron-rich silanes and relatively unhindered terminal alkynes, the major product is the (Z)-vinylsi-lane (Scheme 3, B) from apparent unusual trans-addition to the alkyne.22 This observation was followed by important and confusing discoveries. First, rhodium, under appropriate conditions, will catalyze the isomerization of the (Z)-vinylsilane product B to the (ft)-vinylsilane product A.23 Second, rhodium can also catalyze the reverse, contra-thermodynamic reaction of the (ft)-vinylsilane A to the (Z)-vinylsilane B.24... [Pg.791]

HYDROSILYLATION MECHANISM CHALK-HARROD VS. MODIFIED-CHALK-HARROD... [Pg.224]

Using quantum chemical molecular modelling tools we have examined the reaction mechanism of palladium catalyzed hydrosilylation of styrene by the precatalyst system, 1, developed by Togni and co-workers. One fundamental question that we have focused on is whether the reaction proceeds by the classical Chalk-Harrod mechanism or by an alternative mechanism such as the modified-Chalk-Harrod mechanism. In this section, the general features of the catalytic cycle are examined. [Pg.225]

Figure 5. General schemes for the Chalk-Harrod (right) and the modified-Chalk-Harrod (left) mechanisms for the metal catalyzed hydrosilylation of olefins.

Following olefin coordination, the Chalk-Harrod mechanism proceeds by olefin insertion into the M-H bond, whereas with the modified Chalk-Harrod mechanism, olefin coordination is followed by insertion into the M-Si bond. This step distinguishes the two mechanisms. Thus, the coordination of styrene to the hydridosilyl complex to form an olefin 7t-complex may be the first step of the catalytic cycle that discriminates between the two mechanisms. We have examined this coordination process as well as the relative energies of the many isomers of the 7i-complex that are possible. [Pg.227]

The fact that isomers 8a, 8b and 8c are the lowest energy styrene coordinated complexes have potentially important ramifications that concern the modified-Chalk-Harrod mechanism and the regioselectivity observed in the hydrosilylation. With the modified-Chalk-Harrod mechanism olefin insertion into the M-Si bond follows styrene coordination. However, in all three isomers depicted in Figure 8, the coordinated hydride lies between the... [Pg.229]

If we were to assume that the reaction followed the Chalk-Harrod mechanism, then insertion of the olefin into the Pd-hydride bond in all three isomers 8a-c would lead to the correct regioisomer product. Thus, to some degree the regioselectivity of the hydrosilylation in this catalyst system is determined in the styrene coordination step. We will discuss the origin of the regioselectivity in more detail in Section 4. [Pg.230]

The final step of the Chalk-Harrod mechanism that is distinct from the modified Chalk-Harrod mechanism is the reductive elimination to yield the product. For this step, we have only examined the reductive elimination from the most stable ri-allyl complex lOa-anti. [Pg.234]

A Computational Exploration of the Modified-Chalk-Harrod Mechanism... [Pg.235]

Figure 13. Calculated reaction profile for the silylmetallation process required for the modified-Chalk-Harrod hydrosilylation mechanism.

According to our simulations, hydrosilylation reaction proceeds through the classic Chalk-Harrod mechanism as depicted on the right-hand-side of Figure 5. The modified or anti-Chalk-Harrod mechanism is hindered by a rather large silylmetallation barrier which is calculated to be 46 kcal/mol for the minimal QM model A. [Pg.236]

In the calculations performed with model B the to-7i-complex is destabilized by 1.6 kcal/mol with respect to the corresponding endo isomer. If we were to follow the more stable endo rc-complex isomer through the Chalk-Harrod mechanism, this would lead to the R form of the product as shown on the left-hand-side of Figure 15. Since it is actually the S form of the product that dominates when styrene is the substrate, the formation of the tt-complex cannot be the stereodetermining step of the catalytic cycle. [Pg.242]

As an inversion of enantioselectivity was observed experimentally for 4-(dimethylamino)styrene, (64% R ee) as compared to styrene (64% S ee), we have recalculated the relative thermodynamic stabilities of endo and exo isomers for each step of the catalytic cycle using this second substrate. These calculations allow us to verify the quality of our findings by checking if an inversion in the relative stabilities of the endo and the exo-ri3-silyl-allyl intermediates (with the endo being more stable than the exo) is observed with 4-(dimethylamino)styrene. Using 4-(dimethylamino)styrene as the substrate, the calculated relative stabilities of the intermediates in the Chalk-Harrod mechanism are shown as parenthetic values in Figure 15. [Pg.244]

Metal chemical shifts have not found extensive use in relation to structural problems in catalysis. This is partially due to the relatively poor sensitivity of many (but not all) spin 1=1/2 metals. The most interesting exception concerns Pt, which is 33.7% abundant and possesses a relatively large magnetic moment. Platinum chemistry often serves as a model for the catalytically more useful palladium. Additionally, Pt NMR, has been used in connection with the hydrosilyla-tion and hydroformylation reactions. In the former area, Roy and Taylor [82] have prepared the catalysts Pt(SiCl2Me)2(l,5-COD) and [Pt()i-Cl)(SiCl2Me)(q -l,5-COD)]2 and used Pt methods (plus Si and NMR) to characterize these and related compounds. These represent the first stable alkene platinum silyl complexes and their reactions are thought to support the often-cited Chalk-Harrod hydrosilylation mechanism. [Pg.20]

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