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Relevant academic research and scientific papers

(Planar-Chiral) Ferrocenylmethanols: From Anionic Homo Phospho-Fries Rearrangements to α-Ferrocenyl Carbenium Ions

The reaction of FcCH2OH with chlorophosphates gave ferrocenyl phosphates FcCH2OP(O)(OR)2 [Fc = Fe(η5-C5H5)(η4-C5H4)], which readily separate into phosphate anions and ferrocenyl carbo-cations. The latter species undergoes consecutive reactions, for example, electrophilic aromatic substitutions. When nitriles, instead of alcohols, are treated with FcLi or tBuLi and chlorophosphates, chiral-pool based ferrocenylimino phosphoramidates Fc-CR=N-P(O)(OR*)2 are formed, which are promising candidates for anionic homo phospho-Fries rearrangements. Moreover, the sterically demanding chiral chlorophosphate with R* enabled oxidative couplings of the imines to form a diferrocenylazine. Similarly, the reaction of Fc–Li with 9-anthrylnitrile produced a 10-ferrocenyl-substituted product, contrary to a reaction at the C≡N functionality. A planar-chiral ortho-P(S)Ph2-functionalized ferrocenylmethanol also gave carbo-cations under acidic conditions. These species can be sulfurized in a unique way giving thio ethers, whereby the in situ formed 1,2-P(S)Ph2,CH2+ ferrocene cation acts as the sulfur and electron source. However, lowering the substrate concentration prevents sulfur migration, resulting in electrophilic substitution reactions with aromatic solvents. Planar-chiral ferrocenylmethyl thio or anisyl derivatives were applied as ligands in Pd-catalyzed Suzuki–Miyaura C,C cross-couplings for the atroposelective synthesis of hindered biaryls with up to 26 % ee at low catalyst loadings (1 mol-% Pd).

Evaluation of the Transferability of the “Flexible Steric Bulk” Concept from N-Heterocyclic Carbenes to Planar-Chiral Phosphinoferrocenes and their Electronic Modification

The concept of “flexible steric bulk” is discussed at 2-phenylvinyl-1-phosphinoferrocenes. The introduction of freely rotatable 1'-silyl groups increases the catalytic productivity within the synthesis of tri-ortho-substituted biaryls by Suzuki–Miyaura C,C cross-coupling reactions, giving higher yields with 1/4 of catalyst concentration than for the non-silylated derivatives. Electronic modification of the P and the vinyl donor functionalities was investigated by introducing substituents in the para positions of both groups. Therein, electron-withdrawing phosphines increased the yield from 78 to 91 percent for a given biaryl, by changing from a diphenylphosphino to the P(p-CN-C6H4)2 unit. Opposite results, obtained from electron-donating and sterically demanding phosphines, were in accordance with the 1J(31P,77Se) values. However, the electron density of the ferrocenyl backbone, expressed by the redox potential of the first ferrocenyl-related redox process, cannot be correlated with the donor-properties at the P atom. Changing from a PPh2-substituted ferrocene to a (RA)-1,1'-binaphthyl-containing phosphonite, a complex interaction between the axial- and the planar-chiral motifs occurs, resulting a change of the absolute biaryl configuration.

Synthesis of substituted helicenes by Ir-catalyzed annulative coupling of biarylcarboxylic acid chlorides with alkynes

A series of substituted [4] and [5]helicenes were synthesized in moderate to good yields by an Ir-catalyzed annulative coupling of biarylcarboxylic acid chlorides with internal alkynes, which involves facile C-H bond cleavage and decarbonylation. The double annulative coupling of 1, 1′:5′, 1″-ternaphthalene- 2, 2″-dicarboxylic acid dichloride with 4-octyne was also accomplished to give rise to an S-shaped double helicene. Unexpectedly, a π-extended benzofluoranthene-merged [5]- helicene was constructed through the annulative coupling and the successive C(aryl)-C(aryl) bond forming reaction when 1, 1′:4′, 1″-ternaphthalene-2, 2″-dicarboxylic acid dichloride was employed as the substrate. The crystal structure and the optical properties of the latter unique product were also investigated.

Anionic phospho-fries rearrangement at ferrocene: One-pot approach to P,O-substituted ferrocenes

For the first time the anionic phospho-Fries rearrangement has been successfully applied in ferrocene chemistry, giving access to 1,2-P,O-substituted ferrocenes. The 1,3 (O → C)-migration occurs at ferrocenyl phosphates, thiophosphates, phosphite-borane adducts, and phosphinates by treatment with a base such as lithium diisopropylamide at low temperature, whereas the highest yields were obtained starting from diethylferrocenyl phosphate. Complete reduction of the phosphonate to a primary phosphine and subsequent Stelzer P,C cross coupling allowed the synthesis of Fe(η5-C5H3-2-OMe-PPh2) (η5-C5H5) (1). The qualification of 1 as a supporting ligand in palladium-catalyzed Suzuki-Miyaura C,C couplings has been proven by the synthesis of sterically congested tri-ortho-substituted biaryls under mild reaction conditions in good to excellent yields.

A Planar-Chiral Phosphino(alkenyl)ferrocene for Suzuki-Miyaura C-C Coupling Reactions

Planar-chiral phosphinoferrocene [Fe(η5-C5H3-1-PPh2-2-(E)-CH=CHPh)(η5-C5H5)] (4) was applied in the presence of palladium in Suzuki-Miyaura couplings for the synthesis of sterically congested biaryls. The catalytic activity arises from homogeneous palladium phosphine complexes, of which the potential pre-catalyst [Pd(4)2Cl2] was characterized structurally. The catalytic system is excellently suited for the synthesis of tri-ortho-substituted biaryls under mild conditions (0.1 mol-%, 50-100 C), whereas its application towards the synthesis of tetra-ortho-substituted biaryls is quite limited. Comparing the performance of the reaction with 4 as catalyst and a range of substrates with differing ortho substituents suggests that transmetalation is rate determining. Complex (Sp)-4 was used in atropselective couplings, wherein enantioenrichments of up to 36 % were achieved. The stereoselectivity depends to some extent on the steric properties of the boronic acids; however, slight changes at the aryl halides influence the enantioselectivity.

Hindered aryllithium reagents as partners in palladium-catalyzed cross-coupling: Synthesis of tri- and tetra-ortho-substituted biaryls under ambient conditions

Elegant like a butterfly, stings like a lithium reagent: Mono- and di-ortho-substituted aryllithium reagents were coupled through palladium catalysis with hindered aryl bromides to form highly congested tri- and tetra-ortho-substituted biaryls. The reaction allows the use of easily accessible ortho-functionalized aryllithium compounds. The high reactivity of organolithium reagents facilitates a fast process under ambient conditions.

Synthesis of substituted naphthalenes via a catalytic ring-expansion rearrangement

(Figure Presented) A new methodology for the preparation of substituted naphthalenes starting from readily available indenones, organometal reagents, and trimethylsilyldiazomethane via a catalytic rearrangement process is described. Hindered biaryl naphthalenes, including triortho-substituted biaryls, can be accessed through our method. Our results are consistent with a mechanism involving a benzobenzvalene intermediate.

Efficient synthesis of sterically crowded biaryls by palladium-phosphinous acid-catalyzed cross-coupling of aryl halides and aryl grignards

(Chemical Equation Presented) A series of sterically hindered biaryls have been obtained by palladium- and nickel-phosphinous acid-catalyzed Kumada-Corriu cross-coupling of ortho-substituted aryl halides and Grignard reagents. This method allows formation

Aryl trihydroxyborates: Easily isolated discrete species convenient for direct application in coupling reactions

A conceptually and practically simple alternative approach to the use of arylboron species as the organometallic component in cross-coupling processes is described whereby trihydroxyborate salts are isolated and directly employed. The protocol derives practical benefit from the ease and convenience of the isolation and subsequent use of the discrete borate salts, eliminates the need for additional base, and aids the use of correct reaction stoichiometry.