94372-07-3

Upstream product

• 2443-89-2 1,1-Diiodo-2,2-dimethylpropane 
• 123-72-8 butyraldehyde 
• 3739-96-6 (2,2-Dimethyl-propylidene)-triphenyl-λ⁵-phosphane 
• 95979-33-2 neopentyl triphenylphosphonium bromide 
• 3728-50-5 butylidenetriphenylphosphorane 
• 630-19-3 pivalaldehyde 
• 43216-19-9 Tributylbutylidenphosphoran 
• 128399-08-6 Butylidene-tris-(2-methoxymethoxy-phenyl)-λ⁵-phosphane 
• 94404-12-3 cis-P,P,P-tributyl-3-tert-butyl-4-propyloxaphosphetane 
• 62946-91-2 1-bromo-4,4-dimethyl-2-pentene 
• 925-90-6 ethylmagnesium bromide 
• 630-17-1 2,2-dimethylpropyl bromide 
• 917-54-4 methyllithium 
• 88106-32-5 1-bromo-1-cyclopropyl-2,2-dimethylpropane 

Relevant academic research and scientific papers

Copper-free asymmetric allylic alkylation with grignard reagents

(Chemical Equation Presented) Open wide and say AAA: The copper-free asymmetric allylic alkylation reaction of Crignard reagents, catalyzed by N-heter-ocyclic carbenes, is reported for allyl bromide derivatives. This reaction offers good enantioselectivit

Novel ortho-Alkoxy-Substituted Phosphorus Ylides and Their Stereoselectivity in Wittig Reactions

The stereochemistry of the reactions between tris(2-methoxymethoxypheny)phosphonioethanide (1f), -butanide (2f), and -phenyl-methanide (3f) and a variety of aldehydes was investigated.Ylides having a β-unbranched aliphatic sidechain, such as 2f, and saturated straight-chain aldehydes give olefins with unprecedented cis-selectivity (cis/trans ca. 200:1).

Untersuchungen im Wittig-System nach einem ordnenden Konzept auf der Basis alternativer Prinzipien

Our results show that the stereoselectivity of the Wittig-reaction can be controlled by the variation of substituents in accord with the ORDERING CONCEPT OF ALTERNATIV PRINCIPLES (individual pairs, known and unknown classes of alternatives).The "all-phenyl Wittig-system" having three phenyl groups on phosphorous two in ylid- and aldehyd-position was chosen as a standard for our investigations.Differentiation in ylid-position and compensation on phosphorous and aldehyd-position were observed by the comparison of "patterns".Consequently, most of the selectivity rules of Wittig-reactions can be explained by the differentiation through alternatives in the ylid-position.Inversion or conservation of the "patterns" of measured data points to the variation in structure of starting materials, reaction rates and selectivities.Amount-controls were also described in certain systems.

NMR RATE ON THE WITTIG REACTION OF 2,2-DIMETHYLPROPANAL AND TRIBUTYLBUTYLIDENEPHOSPHORANE

The fate of intermediate oxaphosphetanes in the reaction of t-BuCHO and Bu3P=CHPr was monitored with time.Cis oxaphosphetane 1a was converted to trans oxaphosphetane 1b at -55 deg C with k3=1.5E-4 s-1, and 1b was converted to Bu3P=O and alkene 2b at -15 deg C with k6=2.7E-5 s-1 (t1/2=7.0 h).

HOMOALLYLIC SUBSTITUTION REACTIONS OF LITHIUM DIALKYL CUPRATES WITH CYCLOPROPYLCARBINYL HALIDES: MECHANISTIC CONSIDERATIONS

Highly reactive lithium dialkyl cuprates and 1-bromo-1-cyclopropylalkanes, 4, react to give good yields of the homoallylic substitution product, 6.Less reactive organocuprates react with 4 to give mixtures of 6 and the direct substitution product 7.These results are consistent with a copper(I) radical intermediate which undergoes facile rearrangement prior to reductive coupling.