34697-70-6

Upstream product

• 119841-37-1 2-iodo-3-dimethyl(phenyl)silylpropene 
• 74-88-4 methyl iodide 
• 463-49-0 1,2-propanediene 
• 3839-31-4 dimethyl(phenyl)silyllithium 
• 1458-98-6 2-methyl-3-bromo-1-propene 
• 91076-17-4 dimethyl(phenyl)(prop-1-en-2-yl)silane 

Downstream Products

• 140-29-4 phenylacetonitrile 
• 212388-61-9 (S)-3-(3-Methyl-1-phenyl-but-3-enyloxy)-4-((2R,4R)-2-phenyl-[1,3]dioxan-4-yl)-butan-1-ol 
• 212388-62-0 (R)-3-(3-Methyl-1-phenyl-but-3-enyloxy)-5-((2R,4S)-2-phenyl-[1,3]dioxan-4-yl)-pentan-1-ol 
• 187862-60-8 (4S,5S,6S,9R)-6-Benzyloxy-9-(tert-butyl-diphenyl-silanyloxymethyl)-2,5-dimethyl-undec-1-en-4-ol 
• 212615-45-7 (2R,4R)-4-isopropyl-2-phenyl-1,3-dioxane 
• 212615-52-6 (2R,4S)-2-phenyl-4-(2-phenylethyl)-1,3-dioxane 

Relevant academic research and scientific papers

Silicon Grignard Reagents as Nucleophiles in Transition-Metal-Catalyzed Allylic Substitution

A broad range of transition-metal catalysts is shown to promote allylic substitution reactions of allylic electrophiles with silicon Grignard reagents. The procedure was further elaborated for CuI as catalyst. The regioselectively is independent of the leaving group for primary allylic precursors, favoring α over γ. The stereochemical course of this allylic transposition was probed with a cyclic system, and anti -dia-stereoselectivity was obtained.

Functionalised allylsilanes from silylcopper reagents and allene. A useful strategy for cyclopentane annulations

Silylcupration of allene using phenyldimethylsilylcopper or t- butyldiphenylsilylcopper followed by reaction with α,β-unsaturated acyl chlorides, aldehydes or ketones affords allylsilane-containing divinyl ketones and oxoallylsilanes, respectively. They u

New findings on the regiochemistry of the silylcupration of allene

Allene 1 reacts at -40*C with the phenyldimethylsilylcopper reagent 6, with the opposite regioselectivity to that shown by the corresponding silylcuprate reagent 2, to give allylsilanes 7 and 10-15 rather than vinylsilanes.

THE SILYL-CUPRATION AND STANNYL-CUPRATION OF ALLENES

The stoichiometric silyl-cupration of allene 7, followed directly by treating the intermediate cuprate with a proton, with a range of carbon electrophiles, and with chlorine gives the vinylsilanes 8-13.Alternatively, when iodine is the electrophile, the product is the vinyl iodide 16.This can then be metallated and treated with a proton or a range of carbon electrophiles to give the allylsilanes 18-21.More-substituted allenes also undergo silyl-cupration followed by protonation, phenylallenes giving vinylsilanes, and alkylallenes giving, on the whole, allylsilanes.Stoichiometric stannyl-cupration of allenes takes place, with similar but less reliable regiocontrol to that of the corresponding silyl-cupration.

SILYL-CUPRATION OF ALLENE. A NEW ROUTE TO SILYLATED SYNTHONS

Silyl-cupration of allene followed by treatment with iodine anomalously gives the vinyl iodide 4, a versatile synthetic intermediate.