Asymmetric Total Synthesis of (+)-Chuanxiongnolide L1 via a Stereoselective Oxidative Dearomatization/Diels-Alder Strategy.

The first asymmetric total synthesis of chuanxiongnolide L1 was achieved in 16 steps and 1.9% overall yield by employing a bioinspired chiral auxiliary strategy. The key steps involving asymmetric oxidative dearomatization of chiral amino ether and subsequent asymmetric Diels-Alder reaction of the resulting masked chiral ortho-benzoquinone were adopted.

Access to Fully Substituted Dihydroindazoles Via Hexadehydro-Diels-Alder/[3 + 2] Cycloaddition.

A cascade hexadehydro-Diels-Alder (HDDA)/[3 + 2] cycloaddition reaction between tetrayne and N,N'-cyclic acylhydrazone is described. This strategy allows the efficient construction of fully substituted 2,3-dihydro-1H-indazole scaffolds which have insecticidal activity against the third instar larvae of Mythimna separata.

Furan Synthesis via a Tandem 1,2-Acyloxy Migration/[3 + 2] Cycloaddition/Aromatization of Enol Ether-Tethered Propargylic Esters.

An effective method for the synthesis of furans is developed via a tandem 1,2-acyloxy migration/intramolecular [3 + 2] cycloaddition/aromatization of enol ether-tethered propargylic esters. The reaction exhibits excellent functional group tolerance, broad substrate scope, and excellent chemoselectivity. The isolation of dihydrofuran intermediates in some cases gives more insight into the [3 + 2] cycloisomerization process.

Synthesis of the [6.6.7.5] Tetracyclic Core of Calyciphylline N via a Boc-Mediated Oxidative Dearomatization/Diels-Alder Approach.

A sequential process involving Boc-mediated oxidative dearomatization and inter/intramolecular Diels-Alder reaction was investigated. Based on an intermolecular Diels-Alder reaction and subsequently a radical 7-endo-trig type cyclization, the [6.6.7.5] tetracyclic core of Calyciphylline N was assembled.

Silver Catalyzed Decarbonylative [3 + 2] Cycloaddition of Cyclobutenediones and Formamides.

As an important moiety in natural products, N,O-acetal has attracted wide attention in the past few years. An efficient method to construct N,O-acetal has been developed. Using silver catalyst, cyclobutenediones were smoothly converted to the corresponding γ-aminobutenolides in the presence of formamides, in which cyclobutenediones likely proceed with a key decarbonylative [3 + 2] cycloaddition process. In this way, a series of products with varied substituents were isolated in moderate yield and fully characterized.

Total Synthesis of Caesalpinnone A.

Total synthesis of caesalpinnone A was achieved in 12 steps starting from resorcinol. Key features of the synthesis include BINOL-phosphoric acid catalyzed [4 + 2] cycloaddition, trans-selective nucleophilic substitution, deallylation/oxa-Michael addition cascade, and late-stage photo-Fries rearrangement.

GaCl3-Catalyzed C-H Cyanation of Indoles with N-Cyanosuccinimide.

An efficient GaCl3-catalyzed direct cyanation of indoles and pyrroles using bench-stable electrophilic cyanating agent N-cyanosuccinimide was achieved and afforded 3-cyanoindoles and 2-cyanopyrroles in good yields and excellent regioselectivities. Notably, this protocol exhibited high reactivity for unprotected indoles and was applicable to a broad range of indole and pyrrole substrates.

Dearomatization of Indole via Intramolecular [3 + 2] Cycloaddition: Access to the Pentacyclic Skeleton of Strychons Alkaloids.

An efficient method to build various multisubstituted polycyclic indoline-annulated normal to medium-size rings through dearomatization of indole via a tandem 1,2-acyloxy migration/intramolecular [3 + 2] cycloaddition process is described. The pentacyclic skeleton of strychnine could be synthesized via this tandem cycloaddition and a further Mannich reaction. This approach would provide a novel strategy to the synthesis of strychons alkaloids.

Asymmetric Total Synthesis of Four Stereoisomers of the Sex Pheromone of the Western Corn Rootworm.

A convergent synthesis of four stereoisomers of the sex pheromone of the western corn rootworm (8-methyldecan-2-yl propionate, 1) from commercially available chiral starting materials is reported. The key step was Julia-Kocienski olefination between chiral BT-sulfone and chiral aldehyde. This synthetic route provided the four stereoisomers of 1 in 24-29% total yield via a six-step sequence. The simple scale-up strategy provides a new way to achieve the asymmetric synthesis of the sex pheromone.

Palladium(0)-catalyzed Heck reaction/C-H activation/amination sequence with diaziridinone: a facile approach to indolines.

Indolines are important moieties present in various biologically significant molecules and have attracted considerable attention in synthetic chemistry. This paper describes a Heck reaction/C-H activation/amination sequence for forming indolines using di-tert-butyldiaziridinone. The reaction process likely proceeds via a pallada(II)cycle, which is converted into an indoline by oxidative addition to the diaziridinone and two subsequent C-N bond formations.

Pd(0)-catalyzed sequential C-N bond formation via allylic and aromatic C-H amination of α-methylstyrenes with diaziridinone.

A novel Pd(0)-catalyzed sequential C-N bond formation process via allylic and aromatic C-H amination of α-methylstyrenes with di-tert-butyldiaziridinone, giving spirocyclic indolines in good yields, is described. Four C-N bonds and one spiro quaternary carbon are generated in a single operation.

Stereoselective synthesis of fused spiroindolines via tandem Mannich/intramolecular aminal formation.

A novel tandem Mannich/intramolecular aminal formation between tryptamines and salicylaldehydes was reported. This strategy provides a promising approach for the stereoselective synthesis of a range of complex fused spiroindolines, which bear a highly congested contiguous spiro quaternary center and two tertiary stereocenters, in a highly economical and effective fashion.

Synthesis of the tetracyclic core (ABCE rings) of daphenylline.

A concise synthesis of the tetracyclic core (ABCE rings) of daphenylline has been accomplished involving a benzobicyclo[3.3.1] lactam as the key intermediate. This bridged bicyclic intermediate was efficiently constructed via a Brønsted acid promoted intramolecular Friedel-Crafts type Michael addition of a δ-benzyl α,ß-unsaturated δ-lactam.

Asymmetric total synthesis of cladosporin and isocladosporin.

The first asymmetric total syntheses of cladosporin and isocladosporin were accomplished in 8 steps with 8% overall yield and 10 steps with 26% overall yield, respectively. The relative configuration of isocladosporin was determined via this total synthesis.

Tandem oxidative dearomatization/intramolecular Diels-Alder reaction for construction of the tricyclic core of palhinine A.

A concise construction of the 6/6/5 tricyclic core of Lycopodium alkaloid palhinine A (1) has been accomplished. The developed synthetic strategy featured a tandem oxidative dearomatization/intramolecular Diels-Alder reaction to construct C/D rings and an intramolecular 5-exo-trig radical cyclization to install the B ring of palhinine A (1). The developed approach paves the way for the total synthesis of palhinine A (1).

Au-catalyzed piperidine synthesis via tandem acyloxy migration/intramolecular [3 + 2] cycloaddition of enynyl esters.

An Au-catalyzed tandem protocol involving enynyl ester isomerization and subsequent intramolecular [3 + 2] cyclization has been developed. This strategy provides an efficient approach for the synthesis of polyfunctional piperidines, which are subunits of many bioactive molecules.

PtI2-catalyzed tandem 3,3-rearrangement/Nazarov reaction of arylpropargylic esters: synthesis of indanone derivatives.

An efficient PtI(2)-catalyzed tandem reaction of arylpropargylic esters, involving 3,3-rearrangement and Nazarov reaction, has been developed to produce 3-substituted and 3,3-disubstituted indanone derivatives. This approach provided a pathway to the synthesis of indanone skeletons in natural products.

Total synthesis of (-)-Przewalskin B.

The first total synthesis of (-)-Przewalskin B has been accomplished with an intramolecular nucleophilic acyl substitution (INAS) reaction and an intramolecular aldol condensation as key steps.

Biomimetic total synthesis of (+)-chabranol.

A concise, biomimetic total synthesis of the unprecedented terpenoid skeleton (+)-chabraol has been accomplished via 6 steps from the chiral epoxide 7, involving an intramolecular Prins double cyclization to yield the bicyclo[2.2.1] core of the natural product as the key step. The absolute configuration of natural chabranol was also designated through the first asymmetric total synthesis.