Pd-catalyzed asymmetric intramolecular aryl C-O bond formation with SDP(O) ligand: enantioselective synthesis of (2,3-dihydrobenzo[b][1,4]dioxin-2-yl)methanols. | Semantic Scholar (2024)

Rh-catalyzed asymmetric hydrogenation of various benzo[ b][1,4]dioxine derivatives was successfully developed and applied to develop highly efficient synthetic routes for the construction of some important biologically active molecules, such as MKC-242, WB4101, BSF-190555, and ( R)-doxazosin·HCl.

An enantioselective desymmetric aryl C-O coupling reaction was demonstrated under the catalysis of CuI and a chiral cyclic diamine ligand and a series of chiral oxygen-containing heterocyclic units with tertiary or quaternary stereocarbon centers were synthesized with this method.

A broad range of substrates are compatible with this Cu(I)-diamine catalytic system and afford the desired coupling products with chiral tertiary or quaternary carbon centers in high yields and good to excellent enantioselectivities under mild conditions.

The application of this method to the synthesis of the chiral chroman backbone of α-tocopherol was demonstrated and the sterically bulky and conformationally well defined chiral monophosphorus ligand L4 or L5 was responsible for the high reactivity and enantioselectivity of these transformations.

A highly effective C-O coupling reaction of (hetero)aryl electrophiles with primary and secondary alcohols is reported, affording synthetically important ethers.

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The intramolecular asymmetric aryl C-O coupling reactions of 2-(2-haloaryl)propane-1,3-diols led to the enantioselective formation of chiral (3,4-dihydro-2H-chromen-3-yl)methanols in good yields and high enantiomeric selectivity.

2,3-Dihydro-1,4-benzodioxins can be prepared in a tandem one-pot procedure by reaction of o-iodophenols with epoxides catalyzed by Cu2O/1,10-phenanthroline/Cs2CO3 system, giving moderate to good yields.

DFT studies provide a model which successfully accounts for the origin of enantioselectivity and the cyano group at the prochiral center plays a key role for the high enantiosity and works as an important functional group for further transformations.

A number of oxygen heterocycles were synthesized using the palladium-catalyzed intramolecular etherification of aryl halides by employing di-tert-butylphosphinobiaryl ligands, an antidepressant currently in clinical trials.

It is demonstrated that both 1,2,2-2,6,6-pentamethylpiperidine and 1,4-dioxane can act as hydride donors in palladium-catalyzed polyene cyclizations of 2 and 3 and is the best substitute for PMP.

Pd-catalyzed asymmetric allylic alkylation of the glycine imino ester 1a has been developed using a chiral quaternary ammonium salt 3d without chiral phosphine ligands to achieve high enantioselectivity.

2-Vinylchromanes can be prepared in good yields and high enantiomeric purities from analogous (E)-allylic acetate precursors, which constitutes the first report that acetate is a competent leaving group in COP-catalyzed enantioselective S(N)2' substitution reactions.

The efficient coupling of a number of unactivated aryl chlorides and bromides with cyclic and acyclic secondary alcohols was achieved, including the coupling of allylic alcohols for the first time in a Pd-catalyzed coupling process.

In the presence of (R)-DTBM-SEGPHOS-Pd(OAc)(2) catalyst, N-arylation of various o-tert-butylanilides with p-iodonitrobenzene proceeds with high enantioselectivity to give atropisomeric N-(p-nitrophenyl)anilides having an N-C chiral axis in good yields.

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