Directed regioselective lithiation of (η-arene) chromium tricarbonyl complexes : Regioselective synthesis of anthraquinones and calamenenes

(3-Methoxybenzylalcohol)chromium tricarbonyl (10) and (7-methoxy-1-tetralol)chromium tricarbonyl (12) are selectively lithiated at the 4- and 6-positions, respectively, by treatment with n-BuLi-TMEDA. Since the directed lithiation of the corresponding chromium free arenes normally proceeds at the 2-and 8-positions, complementarily substituted arenes can be prepared by using the chromium tricarbonyl complexes. The difierent position of lithiation is explained by the relative configuration of the chromium tricarbonyl group in the (arene)Cr(CO)₃ and electrostatic factors. Some anthraquinones, 31,36,42, and 7-hydroxycalamenenes, 43, have been synthesized through the stereo- and regioselective introduction of substituents by means of(η⁶-arene)chromium tricarbonyl complexes.     

Selective functionalization of crown ethers via arene chromium tricarbonyl complexes

The crown ethers dibenzo-16-crown-4 and dibenzo-18-crown-5 and a diaryl polyether were complexed by the chromium tricarbonyl group for the purpose of selective functionalization. This complexation did indeed permit exclusive functionalization of the complexed ring. CHO and CH₂OH functionalities were introduced ortho to the ether group. It was noted that the nature of the two ether chains had a strong influence on the regioselectivity of the functionalization, which occurred preferentially on the side with the polyether chain. Photochemical decomplexation produced functionalized organic crown ethers.     

Stereoselective bis-functionalizations of arene chromium tricarbonyl complexes via brook rearrangements

[reaction: see text] An efficient method has been developed for the stereoselective bis-functionalization of arene chromium tricarbonyl complexes. Initial nucleophilic addition of organolithium reagents to a carbonyl moiety is followed by a 1,4-carbon to oxygen silyl migration (Brook rearrangement) and alkylation of the resultant aryl anion.     

Asymmetric synthesis of secondary benzylic alcohols via arene chromium tricarbonyl complexes

(Aryl aldehyde)- and (aryl ketone)-chromium tricarbonyl complexes ortho-substituted with the chiral auxiliary O-methyl-N-(α-methylbenzyl)hydroxylamine undergo diastereoselective addition of Grignard reagents and Super-Hydride^®, respectively, to give the corresponding secondary alcohols in high diastereoisomeric purity. These compounds may be easily decomplexed and deprotected to give the corresponding enantiopure amino alcohols.     

1H NMR conformational analysis of disubstituted arene tricarbonyl chromium complexes

The positions of conformational equilibrium in disubstituted arene chromium tricarbonyl complexes, i.e. alkylanisole chromium tricarbonyl complexes and alkylbenzoate chromium tricarbonyl complexes, have been determined by ¹H NMR spectroscopy. It has been found that the donor effect is the dominant factor in determining the preferred conformation.     

Influence of substituents in tricarbonyl (arene) chromium complexes on the isotopic exchange of hydrogen in an alkaline medium

Russian Chemical Bulletin -     

Asymmetric synthesis of axially chiral benzamides and anilides by enantiotopic lithiation of prochiral arene chromium complexes

Axially chiral benzamides and anilides were prepared by enantiotopic lithiation at the distinguished benzylic methyl of prochiral tricarbonylchromium complexes of N,N-diethyl 2,6-dimethylbenzamide (1) and N-methyl-N-acyl 2,6-dimethylaniline (14 and 21) with a chiral lithium amide base followed by electrophilic substitution in good yields with high optical purity. The resulting axially chiral chromium-complexed benzamides and anilides were oxidized under air to give chromium-free axially chiral benzamides and anilides in an enantiomerically active form without axial bond rotation at room temperature.     

Intramolecular Vinyl Radical Cyclization Reactions of cyclohexadienes derived from sequential additions to (arene)(tricarbonyl)chromium complexes. Preliminary communication

Cyclohexa-1,3-dienes 7–10 with a 1,5,6-substitution pattern were prepared in a one-pot reaction sequence by sequential addition of MeLi and propargyl bromides to the tricarbonylchromium complex 1a . These products were subjected to radical cyclization procedures. Vinyl radical generation by Bu₃Sn addition to the propargyl group in 7–10 was followed by regio- and diastereoselective intramolecular ring closure. Two different 5-exo-trig cyclizations are possible via different vinyl radical intermediates and cyclization to one or the other of the termini of the cyclohexadiene moiety. Internal alkynes reacted to yield exclusively the cis-fused hexahydroindene products 12–14 , whereas the terminal alkyne yielded bicyclo[3.2.1]octenes 11 as sole products.     

Vicinal stereocontrol during nucleophilic addition to arene chromium tricarbonyl complexes: formal synthesis of (+/-)-erythro Juvabione

[reaction: see text] Vicinal stereocontrol during nucleophilic addition of tert-butyl lithiopropionate to eta(6)-anisole chromium tricarbonyl complexes with differing para substituents has been studied. Excellent vicinal double stereoinduction (>99:1) was observed when the para substituent was Si(CH(3))(3), and this has been applied to a stereoselective formal synthesis of (+/-)-erythro Juvabione. Asymmetric synthesis by chiral auxiliary directed nucleophilic addition is also discussed.     

Synthesis and characterization of organometallic conjugated polymers containing tricarbonyl(arene)chromium unit and platinum

Novel organometallic conjugated polymer containing (η⁶-arene)Cr(CO)₃ and platinum in the main chain was synthesized by dehydrohalogenation coupling reaction of (η⁶-1,4-diethynylbenzene)tricarbonylchromium with trans-(PBu₃)₂PtCl₂. The polymer was soluble in common organic solvents and has the number-average molecular weight of 31,000 by GPC analysis. The polymer exhibited an absorption peak derived from π-π^∗ interaction at 358 nm in the UV-Vis spectrum, which showed a red shift of approximately 90 nm compared to that of the model compound. The photochemical ligand exchange reaction of the polymer was also investigated.     

Intramolecular Pd-catalyzed carbocyclization, Heck reactions, and aryl-radical cyclizations with planar chiral arene tricarbonyl chromium complexes

(o-butenylhalobenzene)Cr(CO)(3) complexes were synthesized by diastereoselectve allylmetal additions to o-halo benzaldehyde complexes. The addition of allylZnBr proved particularly convenient and clean. The complexes undergo intramolecular Pd-catalyzed cyclizations (Heck reactions) without decomplexation and/or alkene isomerization. In complexes with a benzylic stereogenic center, the diastereoselectivity of the alkene carbopalladation is governed by the planar chirality of the complex rather than by the benzylic stereogenic center in the side chain. This reaction outcome can be rationalized by the geometry of the arene plane vs that of the Pd coordination plane in the transition step of the alkene carbopalladation step. An alternative cyclization procedure involves the generation of a Cr(CO)(3)-coordinated arene radical from the bromo and iodo complexes. Intramolecular aryl-radical cyclization affords indan complexes. The transition metal arene pi-bond remains intact during this process.     

(Dihydropyridine)iron tricarbonyl complexes

(N-Carboalkoxy-1,2-dihydropyridine)iron tricarbonyl complexes have been isolated by treatment of either N-carboalkoxy-1,2 or -1,4-dihydropyridines with diiron ennecarbonyl. The organic ligand was liberated from these complexes by use of trimethylamine oxide.     

Gold(I)-catalyzed asymmetric synthesis of planar chiral arene chromium complexes

Gold(I)-catalyzed asymmetric cyclization of 1,3-dihydroxymethyl-2-alkynylbenzene chromium complexes gave planar chiral isochromene chromium complexes with high enantioselectivity. Enantiomeric excess of the cyclization products was largely affected by a combination of axially chiral diphosphine(AuCl)(2) precatalysts and silver salts. A system of segphos(AuCl)(2) with AgBF(4) resulted in the formation of the corresponding antipode.     

New planar chiral P,N-ligands containing tricarbonyl(arene)chromium for enantioselective asymmetric hydroboration of styrenes

Optically active (1,2-disubstituted arene) chromium tricarbonyl complexes 2A–2D with a pyridyl and a phosphorus group in the two ortho benzylic positions have been stereoselectively synthesized from a commercially available (+)-(4,6-O-benzylidene)methyl-α-d-glucopyranoside. These chromium complexes have been used as chiral ligands in the preparation of rhodium catalysts for the hydroboration of styrene derivatives. High enantioselectivities were observed in the hydroboration of vinylarenes.     

Synthesis and properties of PPE-type conjugated polymers containing tricarbonyl(arene)chromium unit in the main chain

Novel π-conjugated polymers containing (η6-arene)Cr(CO)₃ in the main chain based on poly(p-phenylene-ethynylene) were prepared by the Sonogashira coupling reaction of η6-(1,4-diethynylbenzene)tricarbonylchromium with 1,4-diiodo-2,5-dialkoxybenzenes. The polymers were soluble in common organic solvents and characterized by NMR and FT-IR spectra. The polymers exhibited an absorption maximum at around 390 nm, which showed a red shift of approximately 30 nm compared to that of the model compound. Cyclic voltammogram showed a single reversible oxidation peak derived from the (η6-arene)Cr(CO)₃ unit.     

Regioselective ortho lithiation of halopyridines

Regioselective ortho lithiation of 2-, 3-, and 4-halopyridines is achieved with lithium diisopropylamide (?78°, tetrahydrofuran) to afford, upon quenching with electrophilic reagents, 2,3- and 3,4-disubstituted pyridines in good to excellent yield.     

Direct synthesis of (η-arene)-tricarbonylchromium complexes by arene displacement from tricarbonyl(η-1-methylpyrrole)chromium(0)

Arene displacement from the title complex occurs under unprecedented mild conditions in neutral media to afford (η⁶-arene)tricarbonylchromium complexes. The process is most effective with heteroaromatic compounds: the first synthesis of a tricarbonyl(η⁶-quinoline)chromium complex and the diastereoselective preparation of a (η⁶-indole) complex derived from L-tryptophan are reported as representative examples.