Sergey K. Moiseev

Benzylic functionalization of (η6-alkylarene)chromium tricarbonyl complexes

Abstract A general method for the regioselective benzylic metallation of (η 6 -alkylarene)chromium tricarbonyl complexes on the action of lithium amides in THF under very mild conditions has been developed. Transmetallation reactions of the lithium derivatives thus obtained produce the corresponding benzylic organotin, zinc and copper chromium tricarbonyl complexes. Methods for the preparative benzylic functionalization of (η 6 -alkylarene)chromium tricarbonyl complexes have been developed, including carboxylation, α-hydroxyalkylation, γ-carbonylation, acylation, arylation, vinylation, heteroarylation and alkylation procedures. 5-Acetoxy-3-benzyl-1,4-methano-2,3,4,5-tetrahydro- IH -3-benzazepine has been prepared using the benzylic lithium derivative of the (η 6 -alkylarene)chromium tricarbonyl complex at the key step. This compound is a representative of the major class of physiologically active compounds known as C -norbenzomorphans.

Structures, dynamic behaviour in solution and cross-coupling reactions of the α-palladiated (η6-alkylarene)tricarbonylchromium complexes containing a palladium-chromium bond

Abstract Structures of the complexes ( η 3 -C 3 H 5 )Pd( μ - η 6:1 -CH 2 Ph Cr ( CO ) 3 and ( η 3 -C 3 H 5 )Pd[ μ - η 6:1 -CH(Ph)Ph]Cr(CO) 3 in solution were evaluated by NMR ( 1 H and 13 C) and IR spectroscopy. The dynamic behaviour of the complexes was investigated. Quick rotation (on the NMR time scale) of the tricarbonylchromium groups around the axis passing through the centre of the η 6 -coordinated phenyl ring and the chromium atom takes place at room temperature and becomes slow on cooling. The η 3 -allylic ligand was proved to undergo no dynamic changes in solution. Unlike the solid state, the semi-bridging carbonyl groups between chromium and palladium atoms are absent or very weak in solution. Cross-coupling reactions of the complexes with organohalides are described.

Arenetricarbonylchromium complexes in the synthesis of 6,7-benzomorphanes

Abstract The action of sodium amide on tricarbonyl-η 6 -[1′,2′,3′,4′-tetrahydro-spiro(1,3-dioxolane-2,1′-naphthalene)]chromium followed by reaction with sodium bromoacetate gives tricarbonyl-η 6 -[1-(1,2,3,4-tetrahydro-4-oxonaphthalene)acetic acid]chromium ( 4 ). Some procedures to transform 4 into 1-( N -benzyl-2-aminoethyl)-1,2-dihydronaphthalene ( 10 )—a synthon to 6,7-benzomorphanes—are described. Cyclization of 10 by action of mercury(II) acetate yields 3-benzyl-1,2,3,4,5,6-hexahydro-1-hydroxy-2,6-methano-3-benzazocine ( 11 ).

Palladium-catalyzed asymmetric allylation and complex formation involving P,N-bidentate derivatives of (S)-2-(anilinomethyl)pyrrolidine

P,N-Bidentate (S)-2-(anilinomethyl)pyrrolidine derivatives and their complexes with rhodium(i) and palladium(ii) were synthesized. It was demonstrated that these compounds can be used in the Pd-catalyzed asymmetric allylation for the synthesis of chiral methyl 2-phenyl-2-(2-phenyl-o-carboranyl-1)pent-4-enoate.

Synthesis ofN-phenyl-substituted derivatives of morphine alkaloids

A method for the preparation ofN-phenyl-substituted morphine alkaloids by treatment of the correspondingN-nor derivatives with Ph3Bi in the presence of Cu(OAc)2 is proposed. 17-Nor-17-phenylthebaine thus obtained can serve as a convenient starting material for the preparation of otherN-phenyl-substituted alkaloids.

Iridium-catalyzed regiospecific allylation of dimethyl malonate in ionic liquids

Allylation of dimethyl malonate with 1-(4-chlorophenyl)prop-2-enyl methyl carbonate in the presence of [Pd(All)Cl]2, [Rh(COD)Cl]2, [Ir(COD)Cl]2 (COD is cycloocta-1,5-diene), and a chiral ferrocenyl-containing phosphite ligand based on (R)-BINOL (BINOL is 2,2′-dihydroxy-1,1′-binaphthyl) in CH2Cl2 gave a mixture of linear and branched cross-coupling products, the latter having a moderate optical purity (below 51%). The rhodium-and iridium-catalyzed reactions were very highly regioselective (regiospecific in the case of Ir), giving a branched product. In ionic liquids ([bmim][BF4] and [bdmim][BF4]) (bmim is 1-butyl-3-methylimidazolium and bdmim is 1-butyl-2,3-dimethylimidazolium), the Ir-catalyzed reaction regiospecifically afforded a branched product as a racemate. The same result was obtained with [Ir(COD)Cl]2 as a catalyst; this reaction easily occurred in ionic liquids even without a base.

Molecular and crystal structures of (6R, 7R, 14S)-6,14-etheno-7-[(1R)-1-hydroxyethyl]- and (6R, 7R, 14S)-6,14-etheno-7-[(1S)-1-hydroxyethyl]-6,7,8,14-tetrahydro-17-nor-17-phenylthebaine

The crystal structures and absolute configurations of (6R,7R,14S)-6,14-etheno-7-[(1R)-1-hydroxyethyl]-6,7,8,14-tetrahydro-17-nor-17-phenylthebaine and (6R,7R,14S)-6,14-etheno-7-[(1S)-1-hydroxyethyl]-6,7,8,14-tetrahydro-17-nor-17-phenylthebaine were established by X-ray diffraction analysis.