65440-74-6

Upstream product

• 65440-76-8 (S_P)-(-)-menthyl methylphenylphosphine oxide 
• 65440-75-7 (R_P)-Menthylmethylphenylphosphine Oxide 
• 75-16-1 methylmagnesium bromide 
• 1610883-70-9 (R_P)-O-(-)-menthyl phenylphosphine oxide 
• 55266-95-0 L-menthylphenylchlorophosphine 
• 16052-42-9 (1R,2S,5R)-menthyl chloride 
• 2216-51-5 (-)-menthol 

Downstream Products

• 65440-75-7 (R_P)-Menthylmethylphenylphosphine Oxide 
• 65440-76-8 (S_P)-(-)-menthyl methylphenylphosphine oxide 

Relevant academic research and scientific papers

Crystallization-Induced Asymmetric Transformation of a Tertiary Phosphine

An equilibrating diastereomer mixture of the tertiary phosphines 5 and 6 (2.5:1 equilibrium ratio) undergoes crystallization-induced asymmetric transformation upon slow evaporation of solvent from refluxing heptane to give a 20:1 ratio in favor of the more stable crystalline isomer 5. The process can also be carried out at room temperature by using iodine to catalyze the interconversion of 5 and 6 via a pentavalent intermediate 8. However, this variation is more sensitive to the purity of the starting phosphine. Crystalline 5 can be converted to the stable borane complex 3, and reductive cleavage of the fluorenyl group using lithium naphthalenide affords the corresponding lithio derivative 10. Alkylation with iodomethane or benzyl bromide affords 13 or 17, respectively, with retention of phosphorus configuration.

Nucleophilic substitution of p-stereogenic chlorophosphines: Mechanism, stereochemistry, and stereoselective conversions of diastereomeric secondary phosphine oxides to tertiary phosphines

A diastereomeric mixture of secondary phosphine oxide is stereospecifically converted to chlorophosphine salt by treatment with oxalyl chloride, which stereoselectively affords P-inverted or retained tertiary phosphines, depending on the substitution with aliphatic or aromatic Grignard reagents, respectively, in high to 99% yield and 99:1 dr. The repulsion of π- electron on aryl to lone electron pair on phosphorus is proposed for the P-retained substitution.

Synthesis of Phosphines Having Chiral Organic Groups Ligated to Chiral Phosphorus

Both R and S phosphorus epimers of menthylmethylphenylphosphine and its phoshine oxide and of neomenthylmethylphenylphosphine and its phosphine oxide were prepared.The menthylmethylphenylphosphine oxides were prepared from neomenthyldiphenylphosphine by a