1.5- silyl shift

Alkali metal derivatives of 2-(trimethylsilyl)aminopyridines can be further derivatized by insertion of 1,3-dicyclohexylcarbodiimide. Functionalized guani-dinates are formed in this reaction via a 1,3-silyl shift. Scheme 170 illustrates the reaction sequence as well as the preparation of an aluminum complex of the modified ligand, which exhibits pseudo jS-diketiminate binding of the metal center, thus exemplifying the coordinative versatility of this new multi-N-donor system. ... 

An interesting [1,3]-Si shift from nitrogen to nitrogen has been observed in the Staudinger imination reaction of AT-ferf-butyl-iV-trimethylsilyl-P,P-di-methyl phosphinous amide 32 with trimethylsilylazide [137]. The steric bulk provided by the tert-hutjl group seems to determine the direction of the silyl shift (Scheme 32). 

Apart from silyl shifts, other reactions that are also characteristic of this class of compounds or their derivatives are due to the easy formation of halogen-silicon bonds. Phosphonium salt 34, resulting from the addition of bromine to 33, undergoes spontaneous desilylation by the action of the bromide anion to give the P-bromophosphazene 35 [138,139] (Scheme 33). 

In the case of silyl-substituted alkynes (R = MejSi), the initially formed irnine undergoes a subsequent 1,3-sigmatropic silyl shift yielding the corresponding enam-ine (Eq. 4.81). 

Scheme 8 [2+3] Cycloaddition of tri-tert-butylphenylphosphaethyne with silyldiazomethane (a) 1,3-silyl shift (b) 1,3-// shift...

Aryl(trimethylsiloxy)carbenes. Acylsilanes (153) undergo a photoinduced C —> O silyl shift leading to aryl(trimethylsiloxy)carbenes (154).73,74 The carbenes 154 can be captured by alcohols to form acetals (157) 73 or by pyridine to give transient ylides (Scheme 29).75 LFP of 153 in TFE produced transient absorptions of the carbocations 155 which were characterized by their reactions with nucleophiles.76 The cations 155 are more reactive than ArPhCH+, but only by factors < 10. Comparison of 154 and 155 with Ar(RO)C and Ar(RO)CH+, respectively, would be of interest. Although LFP was applied to generate methoxy(phenyl)carbene and to monitor its reaction with alcohols,77 no attempt was made to detect the analogous carbocation. 

In a single case, thermal treatment of enone 36 induced a 1,3-sigmatropic silyl shift which led to the formation of the rearranged product 37 (Eq. 8.3) [40], So far, only one example of a ring-opening reaction of a cyclopropane 38 has been reported which furnished tetramethoxy-substituted allene 39 (Eq. 8.4) [41],... 

Trans-1 -allyl-2-(trimethylsilyl)cyclopentane and trans-1 -allyl-2-(trimethylsilyl)-cyclohexane are formed from the reaction of la with cyclopentene and cyclohexene, respectively. A second allylsilylation reaction of these compounds with la also gives unusual allylsilylation products, 7-cyclopent-l-enyl-2,2-dimethyl-4-(trimethylsilyl-methyl)-2-silaheptane (30%) and 4-((cyclohex-l-enyl)methyl)-2,2,8,8-tetramethyl-2,8-disilanonane (39%). As observed in the allylsilylation of 4-(trimethylsilyl-methyl)-l-alkenes, these products are likely formed via intramolecular silyl rearrangements. In this case, the results strongly suggest that a 1,5-silyl shift and... 

Dankwardt s vinylidene-mediated reaction apparently operates concurrently with cationic cycloisomerization to give 3-silyl-l-silyloxy naphthalenes (e.g., 13). From his data, a direct comparison can be made of the effect of different metal complexes and silyl groups on selectivity for a vinylidene-mediated reaction pathway (Table 9.2). At least in this instance, Rh(I) is more vinylidene friendly than Pt(II). Iwasawa and coworkers [7], in an isolated related report, also obtained high selectivity for silyl-shifted products in the presence of a Rh(I)-catalyst, albeit one with a substantially different ligand set from that employed by Dankwardt. 

When phosphaalkynes are exposed to bis- and tris(diazo) compounds, bis- or tris(l,2,4-diazaphosphol-5-yl) compounds are formed that may be further converted into a variety of novel heterocyclic systems. For example, bis- and tris[diazo(tri-methylsilyl)methyl]phosphanes 237 and 240 afforded bis- and tris(diazaphospho-lyl)phosphanes 238 and 241 after cycloaddition with terf-butylphosphaacetylene followed by a subsequent 1,5-silyl shift (Scheme 8.56) (300). Reaction with electrophilic halides at the Wsilyl functions allows the introduction of a heteroatom bridge between the diazaphosphole ring leading to polycyclic ring systems such as 239 and 242. 

The 1,5-cyclization reaction also occurs with (phosphavinyl)diazoalkanes. Thus, (methylenephosphanyl)diazoalkanes 278, generated by electrophilic diazoalkane substitution, readily cyclizes at low temperatures (321,322) (Scheme 8.68). The expected 3//-l,2,4-diazaphospholes 279 were not detected due to their rapid conversion into l//-l,2,4-diazaphospholes 280 by a silyl shift and concomitant aromatization. 

In agreement with the results of experiments on pyrolysis of l,l-bis(trimethyl-silyl)cyclopropane, additional (2/2)CASPT2/6-31G calculations predict that a rapid 1,2-silyl shift will occur in 12a, forming 13a. However, if cis- and trans-l,l-bis(trimethylsilyl)-2,3-dimethylcyclopropanes (11b and 11c) were pyrolyzed, then, as shown in Figure 22.10, the stereochemistry of ring opening could, presumably, still be inferred from the stereochemistry of the double bonds in the expected rearrangement products (13b and 13c). 

In a similar manner, 3,3-disubstituted l,2-bis(trimethylsilyl)cyclopropenes rearrange to l,l-bis(trimethylsilyl)allenes, most likely by 1,2-silyl shift of primarily formed (1-silylvinyl)silylcarbenes. According to ab initio calculations, this reaction pathway is energetically more favorable than those including a 2,2-disilylcyclopropylidene or a 2,3-disilylpropylidene90b. 

Sakurai and coworkers75 generated the five-membered silene 44 by a photochemical 1,3-silyl shift in the cyclic divinyldisilane 45 (Scheme 13). Since the silene 44 is constrained to be planar, no bond rotation is possible during the reaction. Contrary to the previous observations i.e. a simple two-step or a concerted four-centered mechanism, alcohols add to 44 nonstereospecifically, although in the cyclic silene bond rotation is prohibited. 

For l,5-bis(pentamethyldisilanyl)naphthalene a 1,3-silyl migration does not occur. The products formed are analogous to 220 and 225. l-(Pentamethyldisilanyl)naphthalene undergoes silyl migration from position 1 to 8. 2-(Pentamethyldisilanyl)naphthalene 226 gives a silene 227 by a silyl shift from position 2 to 1. It can be trapped in an ene reaction with isobutene to yield 228 (equation 57). 

The regiochemistry of such reactions was further investigated for the dihydropyranyl-substituted phenyldisilane 240134. It was found that two types of silene intermediates, 241 and 242, are formed by 1,3-silyl shifts to the dihydropyranyl and the phenyl group, respectively (equation 60), and that the distribution of trapping products from these silenes depends on the trapping agent used. 

---