Stereoselective synthesis of (Z)-β-fluoro-α,β-unsaturated esters from (Z)-2-fluoro-1-alkenyliodonium salts

(Z)-β-Fluoro-α,β-unsaturated esters were stereoselectively synthesized from (Z)-2-fluoro-1-alkenyliodonium salts by the Pd-catalyzed methoxycarbonylation reaction. The reaction proceeded at room temperature and various functional groups on the substrate can tolerate the reaction conditions.     

The stereoselective synthesis of (Z)-HFCCFZnI and stereospecific preparation of (E)-1,2-difluorostyrenes from (Z)-HFCCFZnI via an unusual Pd(PPh3)4-Cu(I)Br co-catalysis approach or (Z)-HFCCFSnBu3

(Z)-HFCCFZnI was stereoselectively synthesized from activated zinc dust and (Z)-HFCCFI that was synthesized from chlorotrifluoroethene in a sequential manner. Compared to (E)-HFCCFZnI, (Z)-HFCCFZnI was more challenging to prepare in terms of sluggish metallation and formation of by-products, and underwent slower and incomplete Negishi coupling with aryl iodides. In a modification of Negishi coupling, (E)-α,β-difluorostyrenes were stereospecifically prepared in good to excellent yields under mild conditions from aryl iodides and (Z)-HFCCFZnI with the co-catalysis of Pd(PPh₃)₄/Cu(I)Br. Experimental investigation and mechanistic rationalization suggested that Cu(I)Br would be a scavenger of free ligands for the facilitation of Pd(PPh₃)₂ formation, and a supplier of ligand for the metathesis process. Alternatively, (Z)-HFCCFSnBu₃ and aryl iodides with an electron-withdrawing group underwent Stille-Liebiskind coupling to afford (E)-α,β-difluorostyrenes.     

Stereoselective total synthesis of the (Z)-isomer of a novel phytotoxic nonenolide from Phomopsis sp. HCCB03520 and its C-6 epimer

The (Z)-isomer of a phytotoxic nonenolide, (6S,7R,9R)-6,7-dihydroxy-9-propylnon-4-eno-9-lactone isolated from Phomopsis sp. HCCB03520 and its C-6 epimer have been synthesized through a common route starting from butyraldehyde. The synthesis involves enantioselective Maruoka allylation, Sharpless asymmetric epoxidation and intramolecular ring closing metathesis as the important steps.     

Convenient stereoselective synthesis of (Z)-chalcone derivatives from 1,3-diaryl-2-propynyl silyl ethers

Various (Z)-chalcone derivatives were easily synthesized in a stereoselective manner from 1,3-diaryl-2-propynyl silyl ethers by a catalytic reaction using potassium tert-butoxide under very mild conditions after acid treatment.     

Efficient preparation of (Z)-alkenyl derivatives from (Z)-vinyl (N,N-diisopropyl)carbamate via Ni-catalysed coupling reactions

A (Z)-vinyl (N,N-diisopropyl)carbamate treated with Grignard reagents, under Wenkert Nickel-catalysed conditions, gave access to several substituted (Z)-alkenyl derivatives. These Nickel-catalysed reactions, carried out with vinyl-, phenyl-, p-methoxyphenyl-, trimethylsilylmethylmagnesium bromide and benzylmagnesium chloride, led to the corresponding (Z)-alkenyl derivatives in good yields and high stereoselectivities.     

Biotransformation of (+)-(1R,2S)-fenchol by the larvae of common cutworm (Spodoptera litura)

Biotransformation of (+)-(1R,2S)-fenchol by the larvae of Spodoptera litura was carried out. Substrate was converted to three new terpenoids, (+)-(1R,2S)-10-hydroxyfenchol, (+)-(1R,2R,3S)-8-hydroxyfenchol and (−)-(1S,2S,6S)-6-exo-hydroxyfenchol, and one known terpenoid, (−)-(1R,2R,3R)-9-hydroxyfenchol. These structures were established by NMR, IR, specific rotation and mass spectral studies.     

(9Z)-9,13-Tetradecadien-11-ynal, the sex pheromone of the avocado seed moth, Stenoma catenifer

The highly unsaturated aldehyde (9Z)-9,13-tetradecadien-11-ynal and the corresponding alcohol were identified as possible sex pheromone components of the avocado seed moth, Stenoma catenifer. The aldehyde as a single component attracted more male moths than caged virgin female moths, and addition of the analogous alcohol and/or acetate decreased attraction. A stereospecific synthesis of the pheromone is described.     

A highly efficient stereoselective synthesis of (Z)- and (E)-allyl iodides from Baylis-Hillman adducts

A highly efficient synthesis of (Z)- and (E)-allyl iodides has been accomplished by treatment of Baylis-Hillman adducts with iodine and triphenylphosphine in methylene chloride at room temperature. The method is associated with mild reaction conditions, high yields and excellent stereoselectivity.     

Siloxyallenes revisited. A useful functional intermediate for the synthesis of (Z)-β-branched Morita-Baylis-Hillman type adducts and (Z)-chalcones

Siloxyallenes proved to be a useful functional intermediate in the preparation of (Z)-β-branched Morita-Baylis-Hillman type adducts by the reaction of aldehydes with silylacetylenes or siloxypropynes. Various (Z)-chalcones were stereoselectively synthesized from siloxypropynes via siloxyallenes.     

Transition-metal-free synthesis of (Z)-3-ylidenephthalides from 2-acyl-benzoic acids

We report a highly efficient method for the synthesis of (Z)-3-ylidenephthalides via intramolecular cyclization of readily available 2-acyl-benzoic acids mediated by TSTU at room temperature. Using this method, diversely substituted (Z)-3-ylidenephthalides have been generated in good to excellent yields. The application of the method is highlighted by gram-scale preparation of the antiplatelet drug n-butylphthalide.     

Synthesis of (Z)-tributylstannyl enynes: systematic studies of Sonogashira cross-coupling reactions between (E)-1-iodovinyl-1-tributylstannanes and terminal acetylenes using amines or tetrabutylammonium hydroxide (TBAOH) as activator

Sonogashira cross-coupling reactions involving (E)-iodo vinyl stannanes and terminal acetylenes were carried out in the presence of Pd(PPh₃)₄, CuI and several amines, affording (Z)-tributylstannyl enynes in moderate to good yields (62-91%). Utilizing the catalytic system containing Pd(PPh₃)₄ (5%), CuI (10%), and TBAOH (40% in aqueous media) as activator, better yields (72-91%) and lower reaction times were achieved.     

Synthesis of (Z)-1-bromo-1-alkenes and terminal alkynes from anti-2,3-dibromoalkanoic acids by microwave-induced reaction

(Z)-1-Bromo-1-alkenes were stereoselectively prepared in high yields in a short reaction time by microwave irradiation of the corresponding anti-2,3-dibromoalkanoic acids in a Et₃N/DMF system. A one-pot synthesis of terminal alkynes and enynes from 2,3-dibromoalkanoic acids were also developed by microwave-induced reaction.     

An expedient stereoselective synthesis of (Z)- and (E)-allyl iodides from Baylis-Hillman adducts along with selective iodination of benzylic alcohols using the polymethylhydrosiloxane-iodine system

A stereoselective method has been developed for the synthesis of (Z)- and (E)-allyl iodides from Baylis-Hillman adducts using polymethylhydrosiloxane (PMHS) and iodine in chloroform at room temperature. In addition, the reagent system has been utilized for the iodination of benzylic alcohols selectively.     

The stereoselective synthesis of (E)-octafluoro-1,3,5-hexatriene and (3E,5E,7E)-dodecafluoro-1,3,5,7,9-decapentaene

(E)-(1,2-Difluoro-1,2-ethenediyl)bis[tributylstannane], 3, readily undergoes a Pd(PPh₃)₄/CuI-catalyzed cross-coupling reaction with iodotrifluoroethene to yield (E)-octafluoro-1,3,5-hexatriene, 4, in high isomeric purity. (1Z,3E,5Z)-(1,2,3,4,5,6-Hexafluoro-1,3,5-hexenetriyl)bis[tributylstannane], 7, was sequentially prepared from (1Z,3E,5Z)-(1,2,3,4,5,6-hexafluoro-1,3,5-hexenetriyl)bis[triethylsilane], 5, which was prepared via a Pd(PPh₃)₄/CuI-catalyzed cross-coupling reaction of 3 with (E)-1,2-difluoro-1-iodo-2-triethylsilylethene, 6. Pd(PPh₃)₄/CuI cross-coupling of 7 with iodotrifluoroethene gave (3E,5E,7E)-dodecafluoro-1,3,5,7,9-decapentaene, 8.     

A facile approach to spirocyclic butenolides through cascade cyclization/oxidative cleavage reactions of (Z)-enynols catalyzed by gold under dioxygen atmosphere

A facile approach for the syntheses of spirocyclic butenolides through cascade cyclization/oxidative cleavage reactions of (Z)-enynols bearing cyclic substituents at the C-1 position catalyzed by gold under dioxygen atmosphere has been developed. A variety of substituted butenolides was constructed in a regioselective manner from suitably substituted (Z)-2-en-4-yn-1-ols. (Z)-Enynols substituted both at C2 and C3-position afforded the spirocyclic butenolides in moderate to good yields, C-2 unsubstituted (Z)-enynols afforded the products in moderate yields, and the C-3 unsubstituted (Z)-enynols afforded the desired products in low yields.     

Stereoselective preparation of trisubstituted (Z)-alkenes; synthesis of the C17-C27 fragment of (−)-laulimalide

A Ni-catalyzed cross-coupling reaction of (Z)-5-(tert-butyldiphenylsilyl)oxy-3-bromo-1-trimethylsilyl-3-penten-1-yne (1) with alkyl Grignard reagent gives (Z)-3-alkyl-5-(tert-butyldiphenylsilyl)oxy-1-trimethylsilyl-3-penten-1-ynes (2) stereospecifically in good yields. The (Z)-enyne 2a is transformed in four steps to (Z)-3-methyl-5-silyloxy-3-pentenal (3), which is coupled with ketophosphonate 4 to give enone 13. The η-hydroxyallyl methanesulfonate derived from 13 is cyclized to 3,6-dihydro[2H]pyran by an intramolecular SN2′ reaction stereoselectively, furnishing a C17-C27 carbon unit of (−)-laulimalide.     

Improved synthesis of (9Z)-9,13-tetradecadien-11-ynal, the sex pheromone of the avocado seed moth, Stenoma catenifer

The terminal dienyne of (9Z)-9,13-tetradecadien-11-ynal, the sex pheromone of the avocado seed moth, Stenoma catenifer, was constructed by coupling a vinyl iodide precursor with commercially available 1-buten-3-yne with Pd catalysis, resulting in a short and efficient synthesis of the pheromone.     

One-pot synthesis of 1-aryl-3-methyl-1,3-dienes using methallyl(trimethyl)silane and aldehydes and their low temperature (Z)→(E) isomerization induced by sulfur dioxide

2-Methylprop-2-ene-1-sulfonyl fluorides can be easily prepared via the ene reaction of methallylsilanes and SO₂. In the presence of a base, aldehydes and 2-methylprop-2-ene-1-sulfonyl fluorides give 1,3-(E) and (Z)-dienes. Their (Z)→(E) isomerization by classical means fails or leads to their polymerization. It is shown that SO₂ can isomerize 1-aryl-3-methyl-1,3-dienes at low temperature, without formation of sulfolenes (cheletropic addition/elimination). Preliminary mechanistic studies suggest that SO₂ adds to 1,3-dienes forming 1,4-diradical intermediates that are responsible for the (Z)→(E) isomerizations.     

Synthesis of methyl (5Z,8Z,10E,12E,14Z)-eicosapentaenoate

The first total synthesis of methyl (5Z,8Z,10E,12E,14Z)-eicosapentaenoate has been achieved in seven steps and in 16% overall yield. The synthesis confirmed the assigned structure of this polyunsaturated natural product.     

Mild and practical stereoselective synthesis of (Z)- and (E)-allyl bromides from Baylis-Hillman adducts using Appel agents (PPh3/CBr4): a facile synthesis of semiplenamides C and E

Appel agents (PPh₃/CBr₄) have been utilized for high-yielding stereoselective synthesis of (Z)- and (E)-allyl bromides from Baylis-Hillman adducts at room temperature. The method has been applied for the synthesis of naturally occurring bioactive fatty acid amides, semiplenamides C and E.