Synthesis and Absolute Configuration of Diastereomeric Menthyl Benzylphosphinates

Highly Selective 1,4‐ and 1,6‐Addition of P(O)H Compounds to p‐Quinones: A Divergent Method for the Synthesis of C‐ and O‐Phosphoryl Hydroquinone Derivatives

“…> 99:1). [15] As shown in Table 7, a variety of optically pure monosubstituted hydroquinones with P-chiral phosphoryl functionality were readily generated in moderate to excellent yield by simply heating a mixture of chiral H-phosphinate with pquinone in the presence of 0.5 equivalent of water. p-Benzoquinone (1 a), 2,5-dimethyl-1,4-benzoquinone (1 c), 2,5-diphenyl-1,4-benzoquinone (1 e), and naphthoquinone (1 f) could all be used to react with chiral H-phosphinate (R P )-2 h, yielding the corresponding products stereospecifically.…”

Stereoselective Synthesis of Phosphoryl‐Substituted Phenols

“…The metalation‐induced migration of phosphorus from oxygen to carbon atom can be applied to a variety of functionalized optically active phosphonates. According to our previous report,11d we allowed some P ‐chirogenic phosphonates to react with LDA, and the corresponding ( R p)‐phosphoryl‐substituted phenolic compounds were obtained with good to excellent yields (Table 4, entries 1–14). Aryl‐substituted optically active phosphonates bearing different groups such as alkyl, alkoxy, nitro‐ and trifluoromethyl groups all can efficiently undergo the rearrangement to afford the corresponding products in high yields (Table 4, entries 1–10).…”

“…We further operated the reaction of diastereomeric (−)‐menthyl phenyl H ‐phosphinate ( R p/ S p=52/48) with phenol under the Atherton–Todd reaction conditions, and the enantiomer product (−)‐menthyl O ‐phenyl phenyl phosphonate ( 4s , R p/ S p=52/48) was gained in 92% isolated yield 11d. In addition, 2‐hydroxyphenyl (−)‐menthyl phenyl phosphinate ( 5s , R p/ S p=52/48) was also obtained in 95% isolated yield from the reaction of (−)‐menthyl phenyl phenyl phosphonate ( 4s , R p/ S p=52/48) with LDA (Scheme ).…”

“…Based on the present results, a possible mechanism is proposed in Scheme for the lithium‐induced rearrangement reaction. The starting material phenol A reacts with optically active H ‐phosphinates B to generate the P ‐chirogenic phosphonates C with retention of the configuration at the phosphorus center 11d. Through the treatment of LDA, the ortho ‐proton of the aryl ring of P ‐chirogenic phosphonates C is lithiated to form the metalation‐induced intermediate D .…”

General synthesis of P-stereogenic compounds: the menthyl phosphinate approach

“…As mentioned in the introduction, numerous reactions have been described in the literature using (R P )-1, 5c,7,31 and few other menthyl H-phosphinates 5c, 9,32 but to a much lesser extent. In our communication, 10 we also reported various reactions of (R P )-1, such as alkylation and cross-coupling.…”