Chemoselective and Stereoselective
Alcoholysis of
Binaphthyl Phosphonothioates: Straightforward Access to Both Stereoisomers
of Biologically Relevant P‑Stereogenic Phosphonothioates
Posted on 2020-07-13 - 04:38
P-Stereogenic phosphonothioates have attracted
great attention due to their potent biological activities as analogues
of phosphoric acids and phosphorothioates. We demonstrate here straightforward
access to P-stereogenic phosphonothioates through
the use of binaphthyl phosphonothioates as a chiral template. The
first-step alcoholysis of binaphthyl phosphonothioates proceeded via
a transfer of the axial chirality of a binaphthyl group to the central
chirality of a phosphorus atom to give only monoalcohol adducts with
moderate to excellent diastereoselectivities. Further alcoholysis
of the obtained products in the presence of a small excess of alcohol
and base proceeded with complete elimination of a binaphthyl group
to give the corresponding P-stereogenic phosphonothioates
with high enantiomeric excess. A DFT study of the reaction mechanisms
in first-step alcoholysis indicated that the coordination of a sulfur
atom to a sodium cation is the key factor in controlling the diastereoselectivities.
This method can be applied to prepare both stereoisomers of a G6P
analogue with high diastereomeric purity.
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Kuwabara, Kazuma; Maekawa, Yuuki; Minoura, Mao; Maruyama, Toshifumi; Murai, Toshiaki (2020). Chemoselective and Stereoselective
Alcoholysis of
Binaphthyl Phosphonothioates: Straightforward Access to Both Stereoisomers
of Biologically Relevant P‑Stereogenic Phosphonothioates. ACS Publications. Collection. https://doi.org/10.1021/acs.joc.0c00687