Wen-Yong Han

FeCl3-Catalyzed Stereoselective Construction of Spirooxindole Tetrahydroquinolines via Tandem 1,5-Hydride Transfer/Ring Closure

An efficient FeCl(3)-catalyzed stereoselective intramolecular tandem 1,5-hydride transfer/ring closure reaction was developed. The method allows for the formation of structurally diverse spirooxindole tetrahydroquinolines in high yields (up to 98%) with good to excellent levels of diastereoselectivity (up to 99:1 dr). The catalytic enantioselective variant of this process was also investigated preliminarily with a chiral BINOL-derived phosphoric acid.

Highly efficient and stereoselective construction of dispiro-[oxazolidine-2-thione]bisoxindoles and dispiro[imidazolidine-2-thione]bisoxindoles.

An efficient and stereoselective reaction between 3-isothiocyanato oxindoles and isatins/isatinimines has been developed to afford structurally diverse dispiro[oxazolidine-2-thione]bisoxindoles and dispiro[imidazolidine-2-thione]bisoxindoles in excellent results under mild conditions. The potential of asymmetric induction by means of a chiral auxiliary was explored. The isomers are separable, and products could be isolated as single diastereomers by column chromatography. Further synthetic transformations of the reaction product were also successfully realized.

3-isothiocyanato oxindoles serving as powerful and versatile precursors to structurally diverse dispirocyclic thiopyrrolidineoxindoles through a cascade Michael/cyclization process with amino-thiocarbamate catalysts.

Cascading catalysis: 3-Isothiocyanato oxindoles act as powerful and versatile precursors for a range of structurally diverse dispirocyclic thiopyrrolidineoxindoles containing two spiro-quaternary and three contiguous stereogenic centers in quantitative yields with excellent disatereo- and enantioselectivities by only using 1 mol % amino-thiocarbamate catalyst.

Enantioselective synthesis of quaternary 3-aminooxindoles via organocatalytic asymmetric Michael addition of 3-monosubstituted 3-aminooxindoles to nitroolefins.

An enantioselective synthesis of quaternary 3-aminooxindoles with 3-monosubstituted 3-aminooxindoles as nucleophiles is first presented. A Michael addition reaction of 3-monosubstituted 3-aminooxindoles to nitroolefins has been developed with a bifunctional thiourea-tertiary amine as a catalyst to afford a range of 3,3-disubstituted oxindoles bearing adjacent quaternary-tertiary centers in good results (up to 98% yield, >99:1 dr, and 92% ee). We also demonstrate the potential synthetic utility of this methodology by a transformation of the product into a spirocyclic oxindole compound.

Enantioselective Organocatalytic Three-Component Petasis Reaction among Salicylaldehydes, Amines, and Organoboronic Acids

The catalytic enantioselective three-component Petasis reaction among salicylaldehydes, amines, and organoboronic acids with a newly designed thiourea-binol catalyst is presented. A broad range of alkylaminophenols can be obtained in good yield (up to 92%) and good to high enantioselectivity (up to 95% ee). A possible reaction pathway for this catalytic enantioselective Petasis reaction is tentatively proposed.

Organocatalytic enantioselective stereoablative hydroxylation of 3-halooxindoles: an effective method for the construction of enantioenriched 3-substituted 3-hydroxy-2-oxindoles.

3-Substituted oxindoles as electrophilic partners: An unprecedented method for the construction of hydroxylated 3-substituted oxindoles in high yields and excellent enantioselectivities through stereoablative hydroxylation of 3-halooxindoles with an organocatalyst has been developed. This process not only differs from the common convention of using 3-substituted oxindoles as nucleophiles, but also provides a viable entry to optically active 3-substituted 3-hydroxy-2-oxindoles (see scheme).

Asymmetric synthesis of β-hydroxy-α-amino phosphonic acid derivatives via organocatalytic direct aldol reaction of α-isothiocyanato phosphonates with aldehydes.

α-Isothiocyanato phosphonates are first used as nucleophiles to react with aldehydes for the asymmetric synthesis of β-hydroxy-α-amino phosphonic acid derivatives. The process is catalyzed by a quinine-derived thiourea via cascade aldol/cyclization reaction, affording a wide range of protected β-hydroxy-α-amino phosphonates containing adjacent quaternary-tertiary stereocenters in up to 93% yield, up to 81% ee, and >99:1 dr. This work represents the first example of α-isothiocyanato phosphonates serving as nucleophiles that are used in the catalytic asymmetric synthesis.

Chlorophyll a fluorescence responses of Haloxylon ammodendron seedlings subjected to progressive saline stress in the Tarim desert highway ecological shelterbelt

In order to assess the long-term impacts of saline groundwater irrigation to Haloxylon ammodendron, one of the main shrubs in the Tarim desert highway ecological shelterbelt, we irrigated the H. ammodendron seedlings with progressive saline groundwater (3–30 g L−1, simulation environment in the Tarim desert highway ecological shelterbelt) and investigated the diurnal variations of chlorophyll a (Chl a) fluorescence parameters, such as maximal quantum yield of photosystem II (PSII) photochemistry (Fv/Fm), quantum yield of photochemical energy conversion in PSII (YII), the apparent rate of electron transport at the PSII level (ETR), photochemical quenching coefficient (qP), non-photochemical quenching (NPQ), quantum yield of nonregulated non-photochemical energy loss in PSII (YNO) and quantum yield of regulated non-photochemical energy loss in PSII (YII), at approximately 2-h intervals. Fv/Fm with 5 g L−1 (S2) was lower than that with 2 g L−1 (S1) but a little higher than 20 g L−1 (S5), respectively. Under the low light [photosyntheticallyactive radiation (PAR) ≤ 250 μmol m−2 s−1, at 08:00, 10:00 and 20:00 h of the local time], S1 kept the lowest YII and the highest YNPQ; while under the high light (PAR ≥ 1500 μmol m−2 s−1), the YII performed S1>S2>S5, and the reverse YNPQ; under mild light (250 μmol mt-2 s−1 ≤ PAR ≤ 1500 μmol m−2 s−1), S1 remained the highest YII, no matter the light and the salinity, the similar YNO almost occurred basically. The results showed that the sand-binding plant H. ammodendron could regulate its energy-utilizing strategies. The S2 might be the most suitable salinity of the irrigation water for H. ammodendron in the Tarim desert highway ecological shelterbelt in the northwest of China.

A Protocol for the Synthesis of CF2H-Containing Pyrazolo[1,5-c]quinazolines from 3-Ylideneoxindoles and in Situ Generated CF2HCHN2

Herein is disclosed a selective and facile approach for the construction of CF2H-containing pyrazolo[1,5- c]quinazolines from easily accessible 3-ylideneoxindoles and in situ generated CF2HCHN2. The reaction involving a [3 + 2] cycloaddition/1,3-H shift/rearrangement/dehydrogenation cascade proceeded smoothly at room temperature in the absence of catalyst and additive. Moreover, this metal-free process along with mild conditions is desirable and valuable for the pharmaceutical industry. Importantly, this reaction features a broad substrate scope, good functional group tolerance, and gram-scale synthesis.

Organocatalyzed Asymmetric Reaction Using α-Isothiocyanato Compounds

Organocatalyzed asymmetric reaction using α-isothiocyanato compounds has received much attention in the past 5 years, and significant progress has been made for three types of isothiocyanato compounds, including α-isothiocyanato amides, esters, and phospho‐ nates. This chapter covers the recent advances of α-isothiocyanato compounds in the organocatalytic asymmetric reaction.