A palladium-catalyzed hydrocarboxylation of alkynes with formic acid has been developed. The method provides acrylic acid and derivatives in good yields with high regioselectivity without the need to handle toxic CO gas.

A palladium-catalyzed hydrocarboxylation of alkynes with formic acid has been developed. The method provides acrylic acid and derivatives in good yields with high regioselectivity without the need to handle toxic CO gas.

An asymmetric hydrogenation of α-oxymethylcinnamic acids was developed by using chiral spiro phosphine-oxazoline/iridium complexes as catalysts to prepare β²-hydroxycarboxylic acids with high reactivity (TON up to 2000) and excellent enantioselectivity (up to 99.5% ee). By using this highly efficient asymmetric hydrogenation as a key step, a concise total synthesis of natural product homoisoflavone (S)-(+)-4 was accomplished.

A palladium-catalyzed asymmetric OH insertion reaction was developed. Palladium complexes with chiral spiro bisoxazoline ligands promoted the insertion of α-aryl-α-diazoacetates into the OH bond of phenols with high yield and excellent enantioselectivity under mild reaction conditions. This palladium-catalyzed asymmetric OH insertion reaction provided an efficient and highly enantioselective method for the preparation of synthetically useful optically active α-aryl-α-aryloxyacetates.

A highly enantioselective NH insertion reaction of α-diazoketones was developed by using cooperative catalysis by dirhodium(II) carboxylates and chiral spiro phosphoric acids. The insertion reaction provides a new access route to diverse chiral α-aminoketones, which are versatile building blocks in organic synthesis, with fast reaction rates, good yields and high enantioselectivity under mild and neutral conditions.

An efficient catalytic asymmetric hydrogenation of racemic α-arylcyclohexanones with an ethylene ketal group at the 5-position of the cyclohexane ring via dynamic kinetic resolution has been developed, giving chiral α-arylcyclohexanols with two contiguous stereocenters with up to 99% ee and >99:1 cis/trans-selectivity. Using this highly efficient asymmetric hydrogenation reaction as a key step, (−)-α-lycorane was synthesized in 19.6% overall yield over 13 steps from commercially available starting material.

A new and efficient catalytic asymmetric synthesis of the potent cannabinoid receptor agonist (−)-CP-55940 has been developed by using ruthenium-catalyzed asymmetric hydrogenation of racemic α-aryl ketones via dynamic kinetic resolution (DKR) as a key step. With RuCl₂-SDPs/diamine [SDPs=7,7′-bis(diarylphophino)-1,1′-spirobiindane] catalysts the asymmetric hydrogenation of racemic α-arylcyclohexanones via DKR provided the corresponding cis-β-arylcyclohexanols in high yields with up to 99.3% ee and >99:1 cis-selectivities. Both ethylene ketal group at the cyclohexane ring and ortho-methoxy group at the phenyl ring of the substrates 6 have little effect on the selectivity and reactivity of the hydrogenations. Based on this highly efficient asymmetric ketone hydrogenation, (−)-CP-55940 was synthesized in 13 steps (the longest linear steps) in 14.6% overall yield starting from commercially available 3-methoxybenzaldehyde and 1,4-cyclohexenedione monoethylene acetal.

An easily available iron catalyst was developed to accomplish the CH functionalization of indoles with α-aryl-α-diazoesters in high yields under mild conditions. The asymmetric CH functionalization of indoles was also realized by using iron complexes of chiral spiro bisoxazolines with up to 78% ee.

In 2000 China ranked 5^th in the world (7.9%) in the publication of SCI papers on organic synthesis and catalysis; by 2008 China had become 1^st (21.6%), followed by the USA, Germany and Japan. Major contributions made by Chinese research groups in the last decade in the areas of total synthesis of complex natural products, cross-coupling, asymmetric catalysis, and heterogeneous catalysis are highlighted. The output and quality of the research on synthesis and catalysis from China continue to increase, so that with the rapid development of China’s economy, Chinese chemists will make greater contributions to organic synthesis and catalysis in the future.

A highly efficient enantioselective synthesis of chiral β-aryloxy alcohols by the {RuCl₂[(S)-SDP][(R,R)-DPEN]} [(S_a,R,R)-1a; SDP=7,7′-bis(diarylphosphino)-1,1′-spirobiindane; DPEN=trans-1,2-diphenylethylenediamine] complex-catalyzed asymmetric hydrogenation of racemic α-aryloxydialkyl ketones via dynamic kinetic resolution (DKR) has been developed. Enantioselectivities of up to 99% ee with good to high cis/anti-selectivities (up to>99:1) were achieved.

Chiral spiro N,N-diarylphosphoramidites were synthesized. These new chiral spiro monophosphoramidites were efficient ligands for iridium-catalyzed asymmetric hydrogenation of unfunctionalized enamines derived from simple alkyl aryl ketones, providing chiral tertiary amines in good enantioselectivities (up to 90% ee).

Chiral iridium complexes based on spiro phosphoramidite ligands are demonstrated to be highly efficient catalysts for the asymmetric hydrogenation of unfunctionalized enamines with an exocyclic double bond. In combination with excess iodine or potassium iodide and under hydrogen pressure, the complex Ir/(S_a,R,R)-3a provides chiral N-alkyltetrahydroisoquinolines in high yields with up to 98% ee. The L/Ir ratio of 2:1 is crucial for obtaining a high reaction rate and enantioselectivity. A deuterium labeling experiment showed that an inverse isotope effect exists in this reaction. A possible catalytic cycle including an iridium(III) species bearing two monophosphoramidite ligands is also proposed.

A nickel-catalyzed hydrovinylation of α-ketal derivatives of vinylarenes has been developed, providing a new method for preparing functional olefins with a quarternary carbon center in high yields and selectivities.

A new type of recyclable chiral catalyst system was developed by absorption of pyrene-modified Pyrphos rhodium catalyst onto carbon nanotubes via π-π stacking interaction. This modified catalyst was successfully applied in the asymmetric hydrogenation of α-dehydroamino esters for nine cycles without obvious deterioration of activity and enantioselectivity.

A highly efficient copper-catalyzed enantioselective ring opening of oxabicylic alkenes with Grignard reagents has been developed by using chiral spiro phosphine ligands. Excellent trans selectivities, good yields, and high enantioselectivities are obtained for a broad range of Grignard reagents under mild reaction conditions. The catalyst system shows an extraordinary activity and the TON of the reaction reaches 9000.