84491-06-5

Upstream product

• 542-75-6 E/Z-1,3-Dichloropropene 
• 100-52-7 benzaldehyde 
• 107-05-1 3-chloroprop-1-ene 
• 158813-39-9 2-(Z-3-chloroprop-2-enyl)-4,4,5,5-tetramethyl-1,2,3-dioxaborolane 
• 113662-35-4 (Z-3-chloroprop-2-enyl)tri-n-butyl stannane 
• 75927-58-1 2-(1-Chloroprop-2-enyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 
• 67965-28-0 (1-chloroprop-2-enyl)trimethyl silane 

Relevant academic research and scientific papers

Direct synthesis of Z-alkenyl halides through catalytic cross-metathesis

Olefin metathesis has had a large impact on modern organic chemistry, but important shortcomings remain: for example, the lack of efficient processes that can be used to generate acyclic alkenyl halides. Halo-substituted ruthenium carbene complexes decompose rapidly or deliver low activity and/or minimal stereoselectivity, and our understanding of the corresponding high-oxidation-state systems is limited. Here we show that previously unknown halo-substituted molybdenum alkylidene species are exceptionally reactive and are able to participate in high-yielding olefin metathesis reactions that afford acyclic 1,2-disubstituted Z-alkenyl halides. Transformations are promoted by small amounts of a catalyst that is generated in situ and used with unpurified, commercially available and easy-to-handle liquid 1,2-dihaloethene reagents, and proceed to high conversion at ambient temperature within four hours. We obtain many alkenyl chlorides, bromides and fluorides in up to 91 per cent yield and complete Z selectivity. This method can be used to synthesize biologically active compounds readily and to perform site- and stereoselective fluorination of complex organic molecules.

Reactions of α-haloallyllithium derivatives with carbon, silicon, tin or boron halides and carbonyl compounds

A series of allylic halides have been converted into their α-carbanions with strong lithium bases, using different techniques.These have been compared in their reaction with various electrophiles leading to functionally substituted allyl derivatives.The influence of the counterion on the regio- and stereoselectivity has been investigated. allylic halides / α-halocarbanions / allylsilanes / allyltin derivatives / α-chlorohydrins / vinylepoxides / diastereoselectivity

Chloroallyl Anion: Highly Regio- and Diastereoselective α-Addition of Chloroallyl Zinc Reagent to Carbonyl Compounds

The chloroallyl zinc reagent generated insitu by deprotonation of allyl chloride in the presence of lithium diisopropylamide and zinc chloride undergoes highly regio- and diastereoselective α-addition to carbonyl compounds to give syn chlorohydrins which

Stereoselective Synthesis of Alcohols, XXII. E/Z-Selectivity on Addition of α-Substituted Allylboronates to Aldehydes

α-Heterosubstituted allylboronates 7 are prepared.Addition of 7 to aldehydes results in E/Z-isomeric homoallyl alcohols 13 and 14.The reasons for the predominant formation of the Z-isomer 14 are discussed.The Z-bromo olefins 16 and 20 obtained in this way serve as starting point for chain extension or formation of δ-lactones 21.

Z-SELECTIVE FORMATION OF SUBSTITUTED HOMOALLYL ALCOHOLS

The α-substituted allylboronates 4 add to aldehydes giving with high Z-preference the homoallyl alcohols 1.The Z-vinyl bromides obtained were further converted into δ-lactones.

ACTION DU CHLOROALLYLLITHIUM SUR LES ALDEHYDES ET LES CETONES: SYNTHESE EN UNE ETAPE D'ALCOOLS β-ETHYLENIQUES γ-CHLORES DE CONFIGURATION Z ET D'EPOXYDES α-ETHYLENIQUES BI- OU TRI-SUBSTITUES

Chloroallyllithium readily reacts with aliphatic and aromatic aldehydes and ketones to produce, in a one-step reaction, Z-γ-chlorinated-β-ethylenic alcohols and bi- or tri-substituted epoxides.