1,2-Diketones are employed, for the first time, as electrophiles in the vinylogous aldol reaction. With 5 mol% of chiral tertiary amine-thiourea C8, a direct vinylogous aldol-cyclization cascade reaction between β,γ-unsaturated amides and o-quinones has been achieved to produce spirocyclic dihydropyranones in 76–99% yield and 82–95% ee.

A highly enantioselective allylic substitution reaction of anthrones with aromatic or aliphatic allyl carbonates was realized by using iridium catalyst prepared from [Ir(COD)Cl]2 and BHPphos. Substituted 10-allylanthrones were obtained in excellent yields and with excellent enantioselectivity and regioselectivity (up to 98% yield, 99% ee) under mild conditions.Iridium-catalyzed asymmetric intermolecular Friedel–Crafts type allylic substitution reaction of anthrones was developed, affording C10 substituted allylanthrones in good to excellent yields, regioselectivity and enantioselectivity.

A Brønsted acid controlled Diels-Alder reaction of 3-vinylchromones with arynes has been developed. By employing different kinds and amounts of acid, 9-aryl-9H-xanthen-9-ols or ortho-hydroxybenzophenones could be controllably furnished in good yields in an atom- and step-economic manner.

A highly enantioselective Michael addition reaction of α,α-disubstituted aldehydes to β-nitrostyrenes has been developed. In the presence of rosin-based chiral primary amine-thiourea, γ-nitroaldehydes were afforded in excellent enantioselectivities (up to 99 % ee) with up to 99 % yield.

The first organocatalytic enantioselective cascade reaction of Morita–Baylis–Hillman acetates of nitroalkenes with pyrazolones has been developed. With 20 mol % of chiral tertiary-amine squaramide, 1,4,5,6-tetrahydropyrano[2,3-c]pyrazoles were afforded in moderate yields (up to 71%) with excellent stereoselectivities (up to>99:1 dr and up to 98% ee).

Palladium-catalyzed asymmetric intramolecular Friedel–Crafts type allylic alkylation reaction of phenols was developed under mild conditions. In the presence of Pd2(dba)3 with (1R,2R)-DACH-phenyl Trost ligand (L2) in toluene at 50 °C, the reaction provides various C4 substituted tetrahydroisoquinolines with moderate to excellent yields, regioselectivity and enantioselectivity.

An efficient asymmetric vinylogous allylic alkylation of β,γ-butenolides with Morita–Baylis–Hillman carbonates has been developed. With a chiral cyclohexane-based squaramide-phosphine catalyst 5e, optically active γ,γ-disubstituted butenolides containing adjacent quaternary and tertiary chiral centers have been constructed in good-to-excellent yields (up to 98%) and excellent stereoselectivities (87:13–99:1 dr, 96–99% ee).

The direct oxidation of internal alkynes proceeds efficiently in the presence of CuI as a catalyst to afford the corresponding 1,2-diketones in good yields. This strategy offers a simple and efficient route for the synthesis of 1,2-diketones from an inexpensive copper catalyst and easily available internal alkynes. The advantage of present protocol is further demonstrated by the synthesis of quinoxaline derivatives from alkynes and 1,2-diaminobenzene via one-pot procedure.

A highly enantioselective intramolecular Rauhut–Currier reaction of bis(enones) has been developed by employing bifunctional thiourea–phosphine organocatalysts based on a chiral cyclohexane scaffold. In the presence of 10 mol % of thiourea–phosphine 1h, the desired products were obtained in good yields with up to 99% ee.

The direct assembly of benzo[c]carbazole derivatives via the Diels–Alder reaction of arynes and easily accessible 2-alkenylidoles was reported. By employing different aryne precursor loads, 6,7-dihydrobenzo[c]carbazoles or aryl-substituted 7,11b-dihydrobenzo[c]carbazoles could be controllably generated in good to excellent yields under a nitrogen atmosphere. On the other hand, when the reaction was conducted under oxygen, oxidated/aromatized product benzo[c]carbazoles could be generated directly with high selectivity and efficiency in a one-step manner. Interestingly, the benzo[c]carbazole-5-carboxamide amidation derivatives of the above products showed good antitumor activities. The inhibitory effect of these molecules against cancer cells was also described.

New bifunctional phosphines were prepared as chiral organocatalysts for the enantioselective [4+2] cycloaddition between α,β-unsaturated imines and methyl vinyl ketone. In the presence of 10 mol % of amide-phosphine, the [4+2] cycloaddition reaction was achieved in good-to-excellent yields (up to 95%) and diastereoselectivities (up to 99:1 dr) with moderate-to-good enantioselectivities (up to 82% ee). This methodology establishes a new protocol for the asymmetric construction of functionalized tetrahydropyridines.

An effective Friedel–Crafts reaction between N-Boc aminals and N-Boc indoles catalyzed by copper(II) trifluoromethanesulfonate has been developed. The less accessible N-Boc imines could be generated in situ from N-Boc aminals. The reaction was achieved in moderate to good yields under mild conditions.

The first enantioselective vinylogous aldol–cyclization cascade reaction of allyl pyrazoleamides with isatins is reported. With 1 mol% of Takemoto catalyst, optically active spirocyclic oxindole–dihydropyranones were obtained in excellent yields (93–99%) and good-to-excellent enantioselectivities (82–97% ee).

The first enantioselective aza-Morita–Baylis–Hillman reaction of acrylates with ketimines derived from isatins has been developed. With 2 mol% of chiral bifunctional phosphine-squaramide 4e, optically active 3-substituted-3-amino-2-oxindoles were obtained in excellent yields with up to 91% ee.

In this Letter, the α-fluoro-β-amino acid directives were elegantly generated via a novel strategy of the nucleophilic addition of arynes and aziridines. CN bonds were successfully constructed with high efficiency. With the utilization of TABF hydrate as the fluorinated reagent, fluorine atom could be assembled into the target molecule selectively. Interestingly, under another condition, unexpected indole spiro-derivatives could be achieved successfully.

An efficient one-step method has been developed to construct furans via a Suzuki–Miyaura cross-coupling reaction of 1,2-oxaborol-2(5H)-ols with carboxylic anhydrides. In the presence of Pd(OAc)2/PCy3, the multi-substituted alkenylboron compounds could couple with anhydrides to obtain furans in moderate-to-good yields. The addition of bases promoted the coupling reaction, and the plausible reaction mechanism was proposed.

The first organocatalytic enantioselective Mannich reaction of pyrazoleamides with isatin-derived N-Boc ketimines has been developed to afford 2-oxindole-based chiral β-amino amides in good yields (84–97%) with excellent diastereo- and enantioselectivities (up to 99:1 dr and >99% ee).

Phosphine-squaramide derivatives were developed to catalyze the enantioselective Morita–Baylis–Hillman reaction of acrylates with isatins to construct 3-hydroxy-2-oxindoles with quaternary stereocenters. In the presence of 2 mol% H–bonding catalyst 3e, the desired products were achieved in high yields and good-to-excellent enantioselectivities (up to 95% ee).

Novel squaramides containing tertiary phosphine were developed as chiral bifunctional organic catalysts to promote the asymmetric intramolecular Morita–Baylis–Hillman reaction of ω-formyl-enones. The adducts were obtained in high yields with good-to-excellent enantioselectivity (up to 93% ee).

Chiral organophosphine-catalyzed enantioselective Rauhut–Currier reaction has been disclosed for the first time. With L-valine-derived phosphinothiourea, the intramolecular Rauhut–Currier reaction of bis(enones) was achieved in good yields (up to 99%) with excellent enantioselectivities (up to 99.4% ee).

Chiral cyclohexane-based phosphinothioureas were found to be efficient organocatalysts for the enantioselective intramolecular Morita–Baylis–Hillman reaction of ω-formyl-enone. Among the solvents screened, t-BuOH was the best one which provided good yield and enantioselectivity. Moreover in the presence of 3 mol % of phosphinothiourea 2b, the desired products were obtained in good-to-excellent yields with up to 98% ee under mild reaction conditions.(S)-(6-Hydroxycyclohex-1-enyl)(phenyl)methanoneC13H14O2Ee = 85%[α]D25=-36.1 (c 0.42, CHCl3)Source of chirality: asymmetric MBH reactionAbsolute configuration: (S)(S)-(3-Bromophenyl)(6-hydroxycyclohex-1-enyl)methanoneC13H13BrO2Ee = 63%[α]D25=-8.7 (c 0.23, CHCl3)Source of chirality: asymmetric MBH reactionAbsolute configuration: (S)(S)-(4-Bromophenyl)(6-hydroxycyclohex-1-enyl)methanoneC13H13BrO2Ee = 75%[α]D25=-20.0 (c 0.35, CHCl3)Source of chirality: asymmetric MBH reactionAbsolute configuration: (S)(S)-(3-Chlorophenyl)(6-hydroxycyclohex-1-enyl)methanoneC13H13ClO2Ee = 65%[α]D25=-16.3 (c 0.40, CHCl3)Source of chirality: asymmetric MBH reactionAbsolute configuration: (S)(S)-(4-Chlorophenyl)(6-hydroxycyclohex-1-enyl)methanoneC13H13ClO2Ee = 79%[α]D25=-21.3 (c 0.46, CHCl3)Source of chirality: asymmetric MBH reactionAbsolute configuration: (S)(S)-(4-Fluorophenyl)(6-hydroxycyclohex-1-enyl)methanoneC13H13FO2Ee = 83%[α]D25=-31.8 (c 0.33, CHCl3)Source of chirality: asymmetric MBH reactionAbsolute configuration: (S)(S)-(6-Hydroxycyclohex-1-enyl)(naphthalen-2-yl)methanoneC17H12O2Ee = 83%[α]D25=-36.8 (c 0.38, CHCl3)Source of chirality: asymmetric MBH reactionAbsolute configuration: (S)(S)-(6-Hydroxycyclohex-1-enyl)(o-tolyl)methanoneC14H16O2Ee = 66%[α]D25=-7.6 (c 0.46, CHCl3)Source of chirality: asymmetric MBH reactionAbsolute configuration: (S)(S)-(6-Hydroxycyclohex-1-enyl)(m-tolyl)methanoneC14H16O2Ee = 90%[α]D25=-32.0 (c 0.39, CHCl3)Source of chirality: asymmetric MBH reactionAbsolute configuration: (S)(S)-(6-Hydroxycyclohex-1-enyl)(p-tolyl)methanoneC14H16O2Ee = 93%[α]D25=-48.6 (c 0.36, CHCl3)Source of chirality: asymmetric MBH reactionAbsolute configuration: (S)(S)-(6-Hydroxycyclohex-1-enyl)(4-methoxyphenyl)methanoneC14H16O3Ee = 97%[α]D25=-51.0 (c 0.31, CHCl3)Source of chirality: asymmetric MBH reactionAbsolute configuration: (S)(S)-(4-(Dimethylamino)phenyl)(6-hydroxycyclohex-1-enyl)methanoneC15H19NO2Ee = 98%[α]D25=-55.2 (c 0.30, CHCl3)Source of chirality: asymmetric MBH reactionAbsolute configuration: (S)(S)-(6-Hydroxycyclohex-1-enyl)(thiophen-2-yl)methanoneC11H12O2SEe = 76%[α]D25=-40.4 (c 0.26, CHCl3)Source of chirality: asymmetric MBH reactionAbsolute configuration: (S)

A new type of chiral bifunctional phosphinothiourea derived from l-valine is synthesized and used as an organocatalyst in the enantioselective Morita–Baylis–Hillman reaction of aromatic aldehydes with acrylates. The desired products were obtained in good enantioselectivities (up to 83% ee) and in excellent yields (up to 96%) under mild reaction conditions.(S)-1-(1-Diphenylphosphino3-methylbutan-2-yl)-3-phenylthioureaC24H27N2PS[α]D25=+32.1 (c 0.7, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (S)(S)-1-(1-Diphenylphosphino-3-methylbutan-2-yl)-3-(4-methoxyphenyl)thioureaC25H29N2OPS[α]D25=+51.0 (c 0.5, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (S)(S)-1-(4-Chlorophenyl)-3-(1-diphenylphosphino-3-methylbutan-2-yl)thioureaC24H26ClN2PS[α]D25=+59.0 (c 0.5, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (S)(S)-1-(3,5-Bis(trifluoromethyl)phenyl)-3-(1-diphenylphosphino-3-methylbutan-2-yl)thioureaC26H25N2F6PS[α]D25=+7.0 (c 0.5, CH2Cl2)Source of chirality: asymmetric synthesisAbsolute configuration: (S)(S)-1-Cyclohexyl-3-(1-diphenylphosphino-3-methylbutan-2-yl)thioureaC24H33N2PS[α]D25=-81.7 (c 0.3, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (S)(S)-1-(1-Diphenylphosphino-3-methylbutan-2-yl)-3-octylthioureaC26H39N2PS[α]D25=-11.0 (c 0.5, CHCl3)Source of chirality: asymmetric synthesisAbsolute configuration: (S)

Enantioselective aldol reaction of ketones with aldehydes catalyzed by (2S,5S)-pyrrolidine-2,5-dicarboxylic acid in the presence of an equal molar amount of Et3N was described. By using the new chiral organocatalyst, the direct aldol condensation products were obtained in reasonable yields and up to 90% ee.(4R)-4-Hydroxy-4-(4-nitrophenyl)-2-butoneC10H11NO4Ee = 65%[α]D20=+35.0 (c 0.2, CHCl3)Source of chirality: asymmetric aldol reactionAbsolute configuration: 4R

Chiral organophosphine-catalyzed enantioselective Rauhut–Currier reaction has been disclosed for the first time. With L-valine-derived phosphinothiourea, the intramolecular Rauhut–Currier reaction of bis(enones) was achieved in good yields (up to 99%) with excellent enantioselectivities (up to 99.4% ee).

An efficient enantioselective synthesis of spiro[indoline-3,4′-pyrano[2,3-c]pyrazole] derivatives by a cascade reaction between pyrazolones and isatylidene malononitriles is described. With only 1 mol% of (DHQD)2PYR, chiral spirooxindole derivatives have been produced in excellent yields (96–99%) with good-to-excellent enantioselectivities (up to 91% ee).

Novel squaramides containing tertiary phosphine were developed as chiral bifunctional organic catalysts to promote the asymmetric intramolecular Morita–Baylis–Hillman reaction of ω-formyl-enones. The adducts were obtained in high yields with good-to-excellent enantioselectivity (up to 93% ee).

1,2-Diketones are employed, for the first time, as electrophiles in the vinylogous aldol reaction. With 5 mol% of chiral tertiary amine-thiourea C8, a direct vinylogous aldol-cyclization cascade reaction between β,γ-unsaturated amides and o-quinones has been achieved to produce spirocyclic dihydropyranones in 76–99% yield and 82–95% ee.

Palladium-catalyzed asymmetric intramolecular Friedel–Crafts type allylic alkylation reaction of phenols was developed under mild conditions. In the presence of Pd2(dba)3 with (1R,2R)-DACH-phenyl Trost ligand (L2) in toluene at 50 °C, the reaction provides various C4 substituted tetrahydroisoquinolines with moderate to excellent yields, regioselectivity and enantioselectivity.

The first enantioselective vinylogous aldol–cyclization cascade reaction of allyl pyrazoleamides with isatins is reported. With 1 mol% of Takemoto catalyst, optically active spirocyclic oxindole–dihydropyranones were obtained in excellent yields (93–99%) and good-to-excellent enantioselectivities (82–97% ee).

The first enantioselective aza-Morita–Baylis–Hillman reaction of acrylates with ketimines derived from isatins has been developed. With 2 mol% of chiral bifunctional phosphine-squaramide 4e, optically active 3-substituted-3-amino-2-oxindoles were obtained in excellent yields with up to 91% ee.