Themed collection Celebrating 70 Years of Shanghai Institute of Organic Chemistry

The novelty and efficiency of the overall synthetic route are the key values being imparted to the younger generation of synthetic chemists. In this Highlights, synthesis of strictamine was tutored to students on the creativity of synthetic design.

Recent advances in direct fluorination of aromatic compounds by copper catalysts have been highlighted.

The discovery of Lu's [3 + 2] cycloaddition reaction is briefly introduced, and the recent important developments and synthetic applications of Lu's [3 + 2] cycloaddition reaction are highlighted and overviewed.

The highly efficient asymmetric reactions of chiral sulfinyl auxiliary, diene ligands and sulfur–olefin ligands are presented.

Axially chiral allenes are an important class of molecules widely existing in nature and also valuable chiral building blocks for organic synthesis. With more and more new protocols for racemic allenes and new chiral ligands being developed, a wide variety of novel and challenging transformations have been recently unveiled for the synthesis of this type of highly versatile compounds. In this review, we present a critical account of the enantioselective synthesis of axially chiral allenes.

Enantioselective allylation is a highly used organic reaction to prepare chiral homoallylic alcohols and amines, which serve as important building blocks in the synthesis of a variety of natural products and pharmaceuticals.

A triplet biradical mediated dimerization–cyclization reaction of isocyanoaryl-tethered alkylidenecyclobutanes to construct macrocyclic skeletons including dihydroquinoline and quinoline units has been reported.

The mechanism of the Cu(I)-catalyzed reductive A³-coupling reaction of terminal alkynes with aldehydes and 3-pyrroline for the synthesis of E-allylic amines has been studied by DFT calculations.

Two new nosiheptide-type compounds isolated from an engineered strain provide insights into the function of the cytochrome P450 oxygenase NocV.

A facile method for the synthesis of seven- and eight-membered ring-containing polycyclic lactams and lactones by visible light photocatalysis has been developed.

Visible-light-induced radical hydrodifluoromethylation of alkenes with the phosphonium salt [Ph₃P⁺CF₂H Br⁻] under transition-metal-free conditions is described.

A novel anti-Markovnikov selective hydroboration of alkenes and alkynes with HBpin using ⁿBuLi as an effective initiator is described.

A novel rhodium(II)-catalyzed divergent intramolecular tandem cyclization of N- or O-tethered cyclohexa-2,5-dienones and 1-sulfonyl-1,2,3-triazole is disclosed, affording cyclopropa[cd]indole and benzofuran derivatives in moderate to good yields.

The first general route for nickel-catalyzed transfer hydrogenation reaction of alkenes and alkynes using water as the hydrogen source has been developed.

A Rh-catalyzed intramolecular cascade decarbonylative coupling reaction of ortho-formyl group-tethered alkylidenecyclopropanes has been developed, affording indene derivatives in moderate to good yields.

Phosphine-catalyzed fixation of CO₂ with γ-hydroxyl alkynone under ambient temperature and pressure was achieved and the first example of chiral phosphine catalyzed kinetic resolution of propargyl alcohols via carbon dioxide fixation was demonstrated.

The synthesis and characterization of a bistrifluoromethylated organocuprate [Ph₄P]⁺[Cu(CF₃)₂]⁻ and its reactions with a variety of activated heteroaryl bromides, chlorides and iodides were described.

We synthesized 38 OSW-1 analogues with 2-acylamino xylose residues and found that the antitumor activities could be greatly enhanced.

The first general and regioselective nickel-catalyzed hydrocyanation of terminal alkenes with Zn(CN)₂ using an air-stable and inexpensive nickel(II) salt as the precatalyst has been developed.

A Rh(I)-catalyzed intramolecular [3 + 2] cycloaddition reaction of yne-vinylidenecyclopropanes has been developed, providing fused [6.5]-bicyclic products in moderate to good yields.

Pd-Catalyzed ring opening coupling reaction of cyclobutanols with propargylic carbonates afforded δ-allenyl ketones efficiently.

An efficient method for the synthesis of optically active N-alkyl aziridines has been realized for the first time by stereospecific reductive cyclization of optically active α-mesylated acetamides. A series of optically active N-alkyl aziridines are prepared in moderate to good yields and excellent ees.

RhCl(PPh₃)₃-catalyzed [4 + 2] intramolecular cycloaddition of allene-1,3-dienes afforded cis-fused [3.4.0]-bicyclic products with three chiral centers in good yields with excellent chemo- and diastereoselectivity.

Palladium-catalyzed regioselective electrocarboxylation of homostyrenyl acetates with CO₂ has been successfully developed, providing α-aryl carboxylic acids with good selectivity and yield.

A palladium-catalyzed allenylation of hydrocycloalk[b]indoles with 2,3-allenyl carbonates provides functionalized allenes containing an indoline.

A facile synthetic method for the preparation of oxazole and 4-amino-isoquinolin-1(2H)-one derivatives has been developed from the reaction of N-(pivaloyloxy)-amides and ynamides by using different metal catalysts.

The photoredox-catalyzed solvent-dependent tri-/di-fluoroethylation of alkenes with sulfonium salts (Ph₂S⁺CH₂R_F TfO⁻) (R_F = CF₃ or HCF₂) is described.

A facile synthesis of 6H-1,3-oxazin-6-ones and 6H-1,3-thiazin-6-ones has been achieved in the base-promoted [3 + 3] cyclization of cyclopropenones and cyclopropenethiones with amides.

Various base-controlled regioselective reactions of β,γ-unsaturated hydrazones with Selectfluor were achieved under transition metal-free conditions.

The utility of Chen's reagent in trifluoromethylation revisited.

“No Catalyst is Better” is confirmed in the hydroxylperfluoroalkylation of styrenes with perfluoroalkyl iodides under irradiation by visible light.

The asymmetric total or formal syntheses of cornolactone A, cornolactone B, brasoside and littoralisone were accomplished in short steps.

The regiodivergent phosphine-catalyzed [3 + 2] cycloaddition of 2-(2,2,2-trifluoroacetyl)phenylamides and alkynones have been achieved through adjusting the acidities of substrates, changing reaction temperature and addition of protic additive H₂O. The detailed mechanism was systematically studied.

An asymmetric total synthesis of (−)-patchouli alcohol was realized featuring an enantioselective organocatalytic [4 + 2] approach to the [2.2.2] bicyclic core.

The Fe-catalyzed insertion of fluoromethylcarbenes including trifluoromethylcarbene and difluoromethylcarbene into X–H (X = Si, C and P) bonds is described.

An efficient method of cobalt-catalyzed allene-hydrosilylation is developed. The less-substituted CC bond was reacted and the reaction demonstrated Z-stereoselectivity.

Trifluoromethyl has been efficiently incorporated into organic skeletons via allene cyclization and C–C bond cleavage.

Co-Catalyzed Z-selective hydrosilylation of terminal alkynes produces (Z)-β-vinylsilanes, which are further converted to (Z)-disubstituted alkenes by Pd-catalyzed cross couplings.

A highly selective copper-catalyzed borylcupration of 1,2-allenylsilanes affords 2-borylallylsilanes with many synthetically attractive functional groups by applying BIPHEP as the ligand has been developed.

The highly efficient asymmetric synthesis of a pair of enantiomers, (S)-(−)-trolline and (R)-(+)-oleracein E, has been achieved in five steps.

Largely π-extended naphthalenediimides were synthesized by using efficient palladium catalyzed C–H/C–H homocouplings, with the yields of up to 94%.

Palladium catalyzed asymmetric allylic amination of 2-diethylphosphonate-substituted allylic acetates in the presence of SKP ligands afforded the corresponding chiral β-aminophosphonates in good yields, high regioselectivities, and excellent enantioselectivities.

Trifluoromethylthiolation of methylenecyclopropanes (MCPs) has been developed by using AgSCF₃/Na₂S₂O₈ as a trifluoromethylthiolation source (SCF₃) to give trifluoromethylthiolated 1,2-dihydronaphthalene derivatives in moderate to good yields.

Six thiostrepton (TSR) analogs, siomycin (SIO) and SIO-Dha2Ser were produced in the engineered TSR-producing strain by using a single “base”-based mutagenesis strategy.

A facile synthetic method to access N-dialkylaminomethyl-2H-1,2,3-triazoles has been developed from N-sulfonyl-1,2,3-triazoles by a base induced reaction. Moreover, 4-phenyl-1H-1,2,3-triazoles can also give the same product even in the absence of a base at high temperature.

Five new C-terminally methylated TSR derivatives that varied in side-ring structure were obtained via the chemical feeding of quinaldic acid analogs to a double-mutant strain ΔtsrB/T.

Co-catalyzed sequential hydroborations of alkyl and aryl alkynes with pinacolborane produce 1,1-diboronate esters with high selectivity and yields.

A ten-step (the longest linear sequence) total synthesis of sespenine was accomplished.

We report herein the asymmetric total synthesis of α-obscurine (1), β-obscurine (2), N-desmethyl-α-obscurine (3), and N-desmethyl-β-obscurine (4).

Intramolecular formal [3 + 2] cycloaddition and C–H functionalization of N-sulfonyl triazoles with indoles have been developed to synthesize potential indole-fused polycycles.

Cu-Promoted coupling reactions of HCFC-123 with terminal alkynes give trifluoroethylated internal alkynes.

A series of P-chiral biaryl phosphonates were efficiently synthesized from diaryl 2-bromo arylphosphonates in high yields (up to 92%) and good enantioselectivities (up to 88% ee) through a palladium-catalyzed desymmetric intramolecular cyclization with a P-chiral biaryl monophosphorus ligand.

A chemoselective and fast decarboxylative allylation is developed by photoredox catalysis to build C(sp³)–allyl bonds under mild conditions.

An efficient asymmetric nickel-catalyzed alkylative alkyne–aldehyde cross-coupling is developed by employing BI-DIME as the P-chiral monophosphorus ligand, allowing rapid access to a series of chiral tetra-substituted olefinic allylic alcohols in high yields and good to excellent ees.

A copper-mediated oxidative coupling of terminal alkynes and TMSCF₂H has been described for the preparation of various difluoromethylated alkynes.

A Pd-catalyzed intermolecular asymmetric hydroamination of styrenes was developed with pyridine-oxazoline as the chiral ligand.

An efficient catalytic enantioselective Nazarov cyclization of divinyl ketoesters is developed using a BOX/Cu(II) catalyst, affording various optically active cyclopent-2-enone esters.

A sequential catalysis involving olefin cross-metathesis/asymmetric intramolecular Friedel–Crafts alkylation of pyrrole derivatives has been developed.

Monolateral and bilateral sulfur-heterocycle fused naphthalene diimides (NDIs) are successfully synthesized from monobromo and dibromo NDIs via nucleophilic aromatic substitution reactions and the subsequent oxidative aromatization processes.

Copper(I)-catalyzed enantioselective hydroboration of 3-aryl substituted cyclopropene-3-carboxylate is described, providing chiral cyclopropylboronates with excellent enantioselectivities (89–95% ee) in moderate to high yields (55–86%).

The first phosphine-catalyzed cyclopropanation reaction via covalent ylide catalysis has been realized with high efficiency in the presence of sidearm-assisted phosphine catalysts.

Monodentate aminocarbene ligands, both NHC and cAAC, are capable of stabilizing low-coordinate iron(I) compounds.

The direct difluoromethylation of electron-poor aryl iodides, as well as heteroaryl and β-styryl iodides, using TMSCF₂H at ambient temperature was developed.

A facile Pd-catalyzed cascade cyclization of N-alkenylamine and pyruvic acids has been developed to construct spiro-N,O-acetals efficiently.

Catalytic asymmetric hydrogenation of α-arylacrylic and β-arylbut-3-enoic acids using Rh(I) complexes of secondary phosphine oxides provided the corresponding chiral acids with up to 97% ee.

A sequential catalysis by combining a Ru catalyst with chiral phosphoric acid has been utilized for N-alkylation of indole.

Transition-metal-free radical azidofluorination of unactivated alkenes was successfully achieved in aqueous solution at room temperature with excellent regioselectivity and functional group compatibility.

The solvent assistance technologies in detecting reactive intermediates in complicated reaction solutions using electrospray mass spectrometry were summarized and discussed.

The gem-difluoroolefination of carbonyl compounds with difluoromethyl 2-pyridyl sulfone (2-PySO₂CF₂H) has been summarized in this tutorial account.

Chiral phosphine, amine or metal catalyzed asymmetric aza-MBH reactions of various imines with different Michael acceptors in recent decades have been discussed and the perspectives offered by these new developments have also been demonstrated.