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The first highly enantioselective intramolecular N−H bond insertion was realized by using copper catalysts modified with chiral spirobisoxazoline ligands, which provides a novel strategy for the synthesis of chiral 2-carboxytetrahydroquinolines. This reaction features fast reaction rate, high yield, high enantioselectivity, and mild reaction conditions.

The method is extended to the preparation of (VI), the key intermediate for the synthesis of (+)-chelidonine (VII).

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 de- veloped to accomplish the CH functionalization of indoles with a-aryl-a-diazoesters in high yields under mild conditions. The asymmetric CH func- tionalization of indoles was also realized by using iron complexes of chiral spiro bisoxazolines with up to 78% ee.

A catalytic asymmetric version of the intramolecular ylide annulation has been developed which affords high ee values and diastereoselectivities and which further shows that spirobiindane-based chiral phosphines can be excellent organocatalysts. Both optically active benzobicyclo[4.3.0] compounds 2 and 2' with three continuous stereogenic centers could be obtained as major products selectively under neutral and mild conditions just by a choice of an additive.

A highly efficient enantioselective synthe- sis of chiral b-aryloxy alcohols by the {RuCl2((S)- SDP)AR,R)-DPEN)} ((Sa,R,R)-1a ;S DP= 7,7'-bis- A)-1,1'-spirobiindane; DPEN = trans-1,2-diphenylethylenediamine) complex-cata- lyzed asymmetric hydrogenation of racemic a- aryloxydiA ketones via dynamic kinetic resolu- tion (DKR) has been developed. Enantioselectivi- ties of up to 99% ee with good to high cis/anti-selec- tivities (up to > 99:1) were achieved.

Chiral iridium complexes based on spiro phosphoramidite ligands are demonstrated to be highly efficient catalysts for the asymmetric hydroge- nation of unfunctionalized enamines with an exocy- clic double bond. In combination with excess iodine or potassium iodide and under hydrogen pressure, the complex Ir/ASa,R,R)-3a provides chiral N-alkyl- Anolines 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 deute- rium labeling experiment showed that an inverse iso- tope effect exists in this reaction. A possible catalytic cycle including an iridiumA species bearing two monophosphoramidite ligands is also proposed.

A catalytic enantioselective hydrogenation of racemic α-aryloxy aldehydes via dynamic kinetic resolution has been developed by using (diamine)(spirodiphosphine)ruthenium(II) chloride [RuCl2(SDPs)(diamine)] catalysts. Employing this new reaction system a variety of optically active β-aryloxy primary alcohols were synthesized in high yields and moderate to good enantioselectivities.

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 racemic 1,1′-spirobitetralin-8,8′-diol (SBITOL) was conveniently synthesized from 3-methoxybenzaldehyde in 26 % yield over 9 steps and resolved via its bis-(S)-camphorsulfonates. The corresponding chiral spirobitetraline monophosphoramidite ligands have been prepared and their rhodium complexes were applied in the asymmetric hydrogenation of dehydroamino esters with good to excellent enantioselectivities (up to 99.3 % ee).

A novel rhodium-catalyzed asymmetric intramolecular Pauson-Khand reaction using a chiral monophosphoramidite ligands is described. In this reaction, an in situ generated catalyst from [Rh(CO) 2 Cl] 2 , the spiro-monophosphoramidite ligand SIPHOS and AgSbF 6 was found to be effective for a series of 1,6-enynes, providing the co-cyclization products in good enantioselectivities (84% ee).

Novel phosphine-imidazolium salts 2 have been synthesized and successfully used in palladium-catalyzed Suzuki cross-coupling. A combination of 0.05 mol % of [Pd(η-C3H5)Cl]2 and 0.1 mol % of 2b in the presence of 2 equivs. of K3PO4 as base provided coupling products in excellent yields in the reaction of aryl bromides and chlorides with aryl boronic acids.

Chiral spiro diphosphines (SDP) are efficient ligands for the Pd-catalyzed asymmetric allylic alkylation of 1,3-diphenyl-2-propenyl acetate with dimethyl malonate and related nucleophiles. The newly synthesized ligand DMM-SDP (1e) with 3,5-dimethyl-4-methoxy groups on the P-phenyl rings of the phosphine shows the highest enantioselectivity (up to 99.1% ee). Diethylzinc as a base is critical for obtaining high enantioselectivity in the allylic alkylation using beta-dicarbonyl nucleophiles. The structure of catalyst [PdCl(2)((S)-SDP)] was determined by single crystal X-ray diffraction. The SDP ligands create an effective asymmetric environment around the palladium, resulting in high enantioselectivities for the asymmetric allylic alkylation reaction.

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.