55848-86-7

Upstream product

• 674-82-8 4-methyleneoxetan-2-one 
• 67-56-1 methanol 
• 104-55-2 3-phenyl-propenal 
• 105-45-3 acetoacetic acid methyl ester 
• 81114-98-9 Chan's diene 
• 74590-73-1 1,3-bis(trimethylsiloxy)-1-methoxybuta-1,3-diene 

Downstream Products

• 103338-09-6 (E)-(3S,5R)-3,5-Dihydroxy-7-phenyl-hept-6-enoic acid methyl ester 
• 103338-09-6 (E)-(3R,5R)-3,5-Dihydroxy-7-phenyl-hept-6-enoic acid methyl ester 

Relevant academic research and scientific papers

Synthesis of multifunctionalized building blocks via vinylogous addition of Chan's diene to carbonyl and carbonyl-related electrophiles, mediated by molecular iodine

The synthesis of multifunctionalized β-ketoesters has been achieved by using molecular iodine as a catalyst under very mild conditions. The vinylogous addition of Chan's diene 1 to carbonyl and carbonyl-related compounds (aldehydes, ketones, imines and acetals) occurred with high efficiencies and with complete γ-selectivity, giving a useful method for the synthesis of interesting libraries of different δ-functionalized β-ketoesters.

Silicon tetrachloride in organic synthesis: New applications for the vinylogous aldol reaction

This paper describes a novel and efficient methodology for vinylogous aldol reactions based on SiCl4 catalysis. According to the nucleophilicity Mayr's scale, vinylogous aldol reaction of Chan's diene proved to be effective by using catalytic amount of SiCl4, without any other promoter. On the contrary, the SiCl4/Lewis base system has been conveniently exploited for the efficient and selective vinylogous reaction of less nucleophilic Danishefsky's diene and 2-trimethylsilyloxyfuran (TMSOF). Indeed, a number of Lewis bases, such as sulfoxides, formamides and phosphoramides have been successfully used as SiCl4 promoters. TMSOF and silyloxydienes, resulting from 2,2,6-trimethyl-[1,3]-dioxin-4-one derivatives, required stoichiometric amount of SiCl4, while vinylogous aldol reaction of Chan's and Danishefsky's dienes took satisfactorily place in the presence of catalytic or sub-stoichiometric amount of catalyst.

Study on an aldol reaction catalyzed by Ti(IV)/calix[n]arene complexes

Ti(IV)/calixarene complexes, formed in situ or previously prepared with standard procedures, can be conveniently used as efficient catalysts in the aldol reaction of Chan's silyloxydiene with a range of aldehydes bearing either activating or deactivating groups, including aromatic, heteroaromatic and α,β-unsaturated ones. The structure of both calixarene ligand and aldehyde, as well as the reaction conditions, strongly influence the efficiency of the reaction. NMR experiments in conjunction with the experimental results suggest that the structure of the catalytic species in the Ti(IV)/calixarene system prepared in situ is strongly dependent on the concentration and temperature adopted.

STUDIES ON THE DIASTEREOSELECTIVE REDUCTION OF β-HYDROXY KETONES TO 1,3-DIOLS WITH COMMON HYDRIDE REAGENTS

Some common reducing agents were employed in the diastereoselective reduction of several β-hydroxy ketones to their corresponding syn-1,3-diols.The use of NaBH4 with a Ti(IV) chelating species produced syn diols with a moderate to good selectivity significantly depending upon the reaction conditions chosen (solvent, temperature, nature of the titanium species).The use of LiAlH4 at low temperature, in the presence of LiI, showed a high selectivity for reduction to syn diols, thus demonstrating a possible chelating role of lithium.Some interesting preliminary results have been also obtained in the diastereoselective reduction of MEM-protected β-alkoxy ketones.