Titanium complexes, alkenyl

Ind-amido titanium complexes with o -alkenyl functions in position 2 of the indenyl ring have been synthesized and characterized. After activation with MAO, these complexes were used as homogeneous and heterogeneous catalysts for the homopolymerization of ethylene and propylene and the co-polymerization of ethylene and 1,7-octadiene.406 A series of alkyl-, u -alkenyl-, and u -phenylalkyl-substituted Cp- and Ind-amido dichloro titanium complexes have been synthesized and characterized. The cj-phenylalkyl-substituted complexes react with LiBu to give metallacycles via a CH activation reaction on the ortho-position of the phenyl group (Scheme 305).741 742 After activation with MAO, these complexes catalyze ethylene polymerizations. The substituents on the aromatic system influence the polymerization activity of the catalysts and the properties of the polyethylene. The u -alkenyl-substituted catalysts show self-immobilization in ethylene polymerization. 

The Sharpless asymmetric epoxidation (sec. 3.4.D.i) exploits this chelation effect because its selectivity arises from coordination of the allylic alcohol to a titanium complex in the presence of a chiral agent. The most effective additive was a tartaric acid ester (tartrate), and its presence led to high enantioselectivity in the epoxidation.23 An example is the conversion of allylic alcohol 40 to epoxy-alcohol 41, in Miyashita s synthesis of the Cg-Ci5 segment of (-t-)-discodermolide.24 in this reaction, the tartrate, the alkenyl alcohol, and the peroxide bind to titanium and provide facial selectivity for the transfer of oxygen from the peroxide to the alkene. Binding of the allylic alcohol to the metal is important for delivery of the electrophilic oxygen and... 

A small number of enantiomerically pure Lewis acid catalysts have been investigated in an effort to develop a catalytic asymmetric process. Initial work in this area was carried out by Narasaka and coworkers using the titanium complex derived from diol (8.216) in the cycloaddition of electron-deficient oxazolidinones such as (8.217) with ketene dithioacetal (8.218), alkenyl sulfides and alkynyl sulfides. Cyclic alkenes can be used in this reaction and up to 73% ee has been obtained in the [2- -2] cycloaddition ofthioacetylene (8.220) and derivatives with2-methoxycarbonyl-2-cyclopenten-l-one (8.221) usingthe copper catalyst generated with bis-pyridine (8.222). Furthermore, up to 99% ee has been obtained in the [2-1-2] cycloaddition of norbornene with alkynyl esters using rhodium/Hs-BINAP catalysts. This reaction is not restricted to the use of transition metal-based Lewis... 

FIGURE 14.7 Structures of mono-Cp titanium complexes 20-23 with an alkyl or alkenyl substituent on the Cp ring. 

Primary 1-lithio-2-alkenyl diisopropylcarbamates are not configurationally stable in solution. However, under properly selected conditions, the ( )-sparteine complex of the 5-enantiomer crystallizes, leading to a second-order asymmetric transformation6 77-78 132. The suspension is converted to the tri(isopropoxy)titanium derivative with inversion of the configuration, which is shown to have enantiomeric purities up to 94% (Section D.l.3.3.3.8.2.3.). 

Table 11.11. 2-Alkenyl-l-(N,N-dibenzylamino)cyclopropanes formed from N,N-dibenzylformamide (48) and titanium-diene complexes generated in situ by ligand exchange.

Reactions of Titanium Carbene Complexes with Carbon—Carbon Double Bonds Table 14.1. Preparation of carbocyclic compounds from alkenyl thioacetals. 

An unusual reductive elimination can ensue from titanacyclobutanes possessing an alkenyl group at the carbon a to the titanium atom. Thus, alkenylcarbene complexes 48, prepared by the desulfurization of (fy-unsaturated thioacetals 49 or l,3-bis(phe-nylthio)propene derivatives 50 with a titanocene(II) reagent, react with terminal olefins to produce alkenylcyclopropanes 51 (Scheme 14.22, Table 14.4) [37]. This facile reductive... 

Chiral Schiff bases derived from salicylaldehyde, when complexed to titanium(IV), catalyse enantioselective addition of diketene (101) to aldehydes (RCHO R = Ph, alkyl, alkenyl) to yield 5-hydroxy-/ -keto esters (102), with up to 84% ee 19... 

C-M bond addition, for C-C bond formation, 10, 403-491 iridium additions, 10, 456 nickel additions, 10, 463 niobium additions, 10, 427 osmium additions, 10, 445 palladium additions, 10, 468 rhodium additions, 10, 455 ruthenium additions, 10, 444 Sc and Y additions, 10, 405 tantalum additions, 10, 429 titanium additions, 10, 421 vanadium additions, 10, 426 zirconium additions, 10, 424 Carbon-oxygen bond formation via alkyne hydration, 10, 678 for aryl and alkenyl ethers, 10, 650 via cobalt-mediated propargylic etherification, 10, 665 Cu-mediated, with borons, 9, 219 cycloetherification, 10, 673 etherification, 10, 669, 10, 685 via hydro- and alkylative alkoxylation, 10, 683 via inter- andd intramolecular hydroalkoxylation, 10, 672 via metal vinylidenes, 10, 676 via SnI and S Z processes, 10, 684 via transition metal rc-arene complexes, 10, 685 via transition metal-mediated etherification, overview,... 

Cross-coupling reactions 5-alkenylboron boron compounds, 9, 208 with alkenylpalladium(II) complexes, 8, 280 5-alkylboron boron, 9, 206 in alkyne C-H activations, 10, 157 5-alkynylboron compounds, 9, 212 5-allylboron compounds, 9, 212 allystannanes, 3, 840 for aryl and alkenyl ethers via copper catalysts, 10, 650 via palladium catalysts, 10, 654 5-arylboron boron compounds, 9, 208 with bis(alkoxide)titanium alkyne complexes, 4, 276 carbonyls and imines, 11, 66 in catalytic C-F activation, 1, 737, 1, 748 for C-C bond formation Cadiot-Chodkiewicz reaction, 11, 19 Hiyama reaction, 11, 23 Kumada-Tamao-Corriu reaction, 11, 20 via Migita-Kosugi-Stille reaction, 11, 12 Negishi coupling, 11, 27 overview, 11, 1-37 via Suzuki-Miyaura reaction, 11, 2 terminal alkyne reactions, 11, 15 for C-H activation, 10, 116-117 for C-N bonds via amination, 10, 706 diborons, 9, 167... 

Finally, insertion of acetylenes into titanium- and zirconium-nitrogen bonds affords isolable alkenyl complexes (54). 

Formation of w-Allylic Complex Followed by Acyldemet-alation. 2-Trimethylsilylmethyl-1,3-butadiene forms a titanium(III) complex by the reaction with dichlorobis-(cyclopentadienyl)titanium and n-PrMgBr. The complex reacts with carboxylic acid chlorides RCOCl (R = alkyl, alkenyl) to give, y-unsaturated ketones (eq 16). ... 

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