2,6-Xylyl isocyanide

Isocyanide is isoelectronic with CO and a reactive compound in the presence of Pd catalysts. The heterobicyclic compound 127 is obtained by the successive insertion of 2.6-xylyl isocyanide (126) into the Pd-hydride bond formed from the hydrosilane[121. Aryl isocyanide inserts into the Si—Si bond in oligo-silanes. For example, 3 mol of 2,6-xylyl isocyanide insert into the tetrasilane 128 to give 129[122],... 

Reaction of [Pt3(/u-S02)3 P(Cy)3 3] with 2,6-xylyl isocyanide results in displacement of one or at most two of the S02 ligands by the isocyanide.21 Similarly, carbon monoxide usually only partially displaces the S02, but the addition of trimethylamine /V-oxide (Me3NO) facilitates the substitution leading to formation of [PtsQx-COjsfPlCyjs js].22 Me3NO also facilitates substitution of one S02 ligand by halides and azide.2... 

Indoles were synthesized by the intramolecular functionalization of a benzylic C-H bond. Hence, the reaction of 2,6-xylyl isocyanide with a ruthenium complex led to 7-methylindole (Equation (36)). 

Insertion of isocyanides into Si-Si bonds of oligosilanes has been examined. For instance, 2,6-xylyl isocyanide inserts into every Si-Si bond of decamethyltetrasilane in the presence of palladium(n) acetate, whereas the use of a more bulky 2,6-diisopropylphenyl isocyanide leaves the central Si-Si bond intact (Scheme 30).133,134... 

Silaboration of 3-substituted 1,2-dienes takes place smoothly at the internal double bond in the presence of the catalytic Pd(acac)2-2,6-xylyl isocyanide complex and the boryl group is regioselectively introduced to the central carbon atom of an allene (Scheme 16.55) [59, 60]. The same regioselectivity is observed with the catalytic system Pd2(dba)3-P(OCH2)3CEt [59]. 

An interesting catalytic indole synthesis was realized by the benzilic C-H bond activation on 2,6-xylyl isocyanide (Eq. 38) [93]. A coordinatively unsaturated... 

Similarly, reactions of Pt(l,5-cyclooctadiene)2 with RNC(R = Me, Et, CeHn, t-Bu) give Pt3(RNC)6. With 2,6-xylyl isocyanide, Pt7(RNC)i2 is isolated this cluster is also prepared by reduction of Pt(2,6-Me2C6H3NC)2Cl2 with sodium amalgam. ... 

The imido titanium complex supported by a diamido-pyridine framework Ti(=NBut)[(2-C5H4N)C(R)-(CH2NSiMe3)2](py) (R = H, Me) reacts with 2,6-xylyl isocyanide to give the double insertion of the isocyanide into the imido titanium bond and formation of the corresponding four-membered titanacycle with one cr-Ti-C bond the... 

The reaction of 25a, containing the aromatic 2,6-xylyl isocyanide ligands, with dimethyl maleate in pentane (Scheme proceeds with stereospecific cyc-... 

Boiylsilylation (borasilylation) of alkylallene 151 with the silylborane 152 provided the 2-boryl-3-silyl-l-alkene 153 regioselectively in 99% yield. Hindered 2,6-xylyl isocyanide (154) was the effective ligand for the reaction [49]. A similarly good result was obtained by using Pd2(dba)3 in eombination with cyclic phosphite (III-2) as a eatalyst [50]. 

The reaction of 2,3-0-cyclohexylidene-D-glyceraldehyde with the o-hydroxyacetyl anion equivalent (4), prepared from benzyl chloromethyl ether, 2,6-xylyl isocyanide and... 

Bond activation by eoordinatively unsaturated metal fragments provides a convenient route to aryl complexes in a number of cases. Thermolysis of [Ru(dmpe)2(GioH8)H] with 1 equiv. of 2,6-xylyl isocyanide at 60 °G generates trans-[Ru(dmpe)2(7-methylindole-6 )H]" 7, whieh undergoes isomerization to the m-isomer 8 upon heating at 100 °G. The... 

Reactions of [Cp Ir(NR)] R = Bu 662a or 2,6-Pr 2C6H3 662b with 2,6-xylyl isocyanide [(Xyl)NG], mesityl isocyanate, and mesityl azide were studied by Danopoulos et The bridged dimers [Cp"lt(/r-NCsFl9)]2... 

An unusual cluster, [Pt7(2,6-Me2CeH3NQi2], which has been structurally characterized, results on reaction of 2,6-xylyl isocyanide with [Pt(cod)2]. ... 

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