Metal-dependent regioselective oxidative coupling of 5,10,15-triarylporphyrins with DDQ-Sc(OTf)3 and formation of an oxo-quinoidal porphyrin

[reaction: see text] Regioselectivity of the oxidative coupling of 5,10,15-triarylporphyrin metal complexes with DDQ-Sc(OTf)(3) was dependent on the central metal and meso-aryl substituent. Oxo-quinoidal porphyrin was obtained from Ni(II) porphyrin under the same conditions.     

Synthetic studies on carbapenem antibiotics from penicillins. IV. Stereoselective kinetic protonation of a chiral azetidinone enolate

A stereoselective kinetic protonation of the azetidinone enolate $\text{B}$ was studied and an efficient synthesis of$\text{2}$(cis) was achieved via aldol reaction of $\text{5}$ with acetone followed by the kinetic protonation with Ph₃SnH as proton source.     

Efficient excitation energy transfer in long meso-meso linked Zn(II) porphyrin arrays bearing a 5,15-bisphenylethynylated Zn(II) porphyrin acceptor

Electronically coupled porphyrin arrays are suitable for artificial light harvesting antenna in light of a large absorption cross-section and fast excitation energy transfer (EET). Along this line, an artificial energy transfer model system has been synthesized, comprising of an energy donating meso-meso linked Zn(II) porphyrin array and an energy accepting 5,15-bisphenylethynylated Zn(II) porphyrin linked via a 1,4-phenylene spacer. This includes an increasing number of porphyrins in the meso-meso linked Zn(II) porphyrin array, 1, 2, 3, 6, 12, and 24 (Z1A, Z2A, Z3A, Z6A, Z12A, and Z24A). The intramolecular singlet-singlet EET processes have been examined by means of the steady-state and time-resolved spectroscopic techniques. The steady-state fluorescence comes only from the acceptor moiety in Z1A-Z12A, indicating nearly the quantitative EET. In Z24A that has a molecular length of ca. 217 A, the fluorescence comes largely from the acceptor moiety but partly from the long donor array, indicating that the intramolecular EET is not quantitative. The transient absorption spectroscopy has provided the EET rates in real time scale: (2.5 ps)(-1) for Z1A, (3.3 ps)(-1) for Z2A, (5.5 ps)(-1) for Z3A, (21 ps)(-1) for Z6A, (63 ps)(-1) for Z12A, and (108 ps)(-1) for Z24A. These results have been well explained by a revised F?rster equation (Sumi formula), which takes into account an exciton extending coherently over several porphyrin pigments in the donor array, whose length is not much shorter than the average donor-acceptor distance. Advantages of such strongly coupled porphyrin arrays in light harvesting and transmission are emphasized in terms of fast EET and a large absorption cross-section for incident light.     

Asymmetric synthesis of permethric acid. stereochemistry of chiral copper carbenoid reaction

The most effective optical isomer (1$\text{R}$-$\text{cis}$) of permethric acid ($\text{2}$, R = H), a potent intermediate in the production of synthetic pyrethroid, was enantioselectively prepared.     

Synthesis,Separation, and Theoretical Studies of Chiral Biphenyl Lignans (α‐ and β‐DDB)

Two biphenyl lignans, α‐ and β‐DDB ( 1 and 2 , respectively) were efficiently synthesized without contamination by other regio‐isomers. The different yields of the Ullmann coupling reactions for the synthesis of 1 and 2 were rationalized by calculating steric hindrance, stability, entropy change, and heat‐of‐formation values. The enantiomers of 1 and 2 were readily separated by HPLC on a chiral stationary phase. Their configurations were assigned based on the Cotton effect of the authentic natural products.     

Cyclopalladated ferrocenylimine as an efficient catalyst for the syntheses of diarylmethane derivatives

The cyclopalladated ferrocenylimine adducts Ia , Ib , Ic were evaluated in the Suzuki cross‐coupling reaction of benzyl halides with arylboronic acids. The tricyclohexylphosphine adduct Ia exhibited highly catalytic activity for the coupling of aryl and heteroaryl boronic acids containing various functional groups with benzylic bromides and chlorides (up to 99% yield), furnishing diarylmethane derivatives with low catalyst loading (1 mol%). It is worth noting that catalyst Ia can be reused eight times without losing its catalytic activity. Copyright © 2012 John Wiley & Sons, Ltd.     

Lewis acid-catalyzed tandem acylation–Nazarov cyclization for the syntheses of fused cyclopentenones

Treatment of N-tosylpyrroles or N-tosylindoles with α-unsubstituted α,β-unsaturated carboxylic acids or unsaturated carboxylic acids having an α electron-withdrawing substituent in the presence of TFAA and a Lewis acid catalyst resulted in the formation of fused cyclopentenones via a tandem acylation–Nazarov cyclization sequence, while either the acylation product obtained or no reaction occurred in the absence of the Lewis acid catalyst.     

Dinuclear zinc catalyzed asymmetric tandem Michael addition/acetalization reactions of cyclic diketones and β,γ-unsaturated α-ketoesters

The dinuclear zinc–ProPhenol complex is applied as efficient catalyst in the highly stereoselective tandem Michael addition/acetalization reactions of cyclic 1,3-diketones and β,γ-unsaturated α-ketoesters. A variety of substrates are well-tolerated, and a broad range of synthetically and pharmaceutically useful chiral chromene derivatives are directly produced in good yields of up to 96% and good enantioselectivities of up to 96% ee.