P-Chiral 1,7-diphosphanorbornenes: from asymmetric phospha-Diels–Alder reactions towards applications in asymmetric catalysis

Abstract

A straightforward synthesis of P-chiral polycyclic phosphines by an asymmetric Diels–Alder reaction of 1-alkyl-1,2-diphospholes and (5R)-(l-menthyloxy)-2(5H)-furanone (MOxF) is presented.

Oxophosphonium-alkyne cycloaddition reactions: reversible formation of 1,2-oxaphosphetes and six-membered phosphorus heterocycles

“…Our computational results indicate that the acyclic 1-phospha-4-oxa-butadiene state of [ 2a ] + is thermally accessible, which prompted us to investigate whether it can be trapped by [4 + 2] hetero Diels–Alder cycloaddition reactions. Similar to α,β-unsaturated carbonyls, which are important dienes in hetero Diels–Alder reactions for material and natural product synthesis, phospha-butadiene derivatives have been used in cycloaddition reactions for the construction of phosphorus-containing heterocycles. − Furthermore, neutral σ 3 λ 5 -phosphoranes containing the PC–­CO system were postulated as reactive intermediates based on their ability to undergo [4 + 2] cycloaddition reactions with polar multiple bonds. , …”

Synthesis of P-stereogenic 1-phosphanorbornane-derived phosphine–phosphite ligands and application in asymmetric catalysis

“…S1 ‡). 26,32,33 The unprotected compound L1 can be obtained by reaction of 7 with either excess of freshly activated Raney nickel (Raney Ni) or with 4-5 eq. of LiAlH 4 at elevated temperatures for 17 h in THF (Scheme 1).…”

Review on asymmetric cycloaddition reactions at phosphorus (III) atom

“…The use of 14 as ligands in the Pd-catalyzed asymmetric allylic alkylation of cinnamyl acetate with cyclic ethyl 2-oxocyclohexane-1-carboxylate and ethyl 2-oxocyclopentane-1-carboxylate provided up to 52% and 47% ee, respectively. 27…”