Rh(iii)-Catalyzed one-pot three-component cyclization reaction: rapid selective synthesis of monohydroxy polycyclic BINOL derivatives

Abstract

Rh(III)-catalyzed three-component C−H bond functionalizational protocol has been successfully applied to access complex polycyclic BINOL derivatives in which the formation of intermediate amides occurred in situ from aldehydes and amines....

Regioselective Substitution of BINOL

“…When (R)-345 is treated with the Rh(III) complex, the ester group of the BINOL can direct an ortho-C−H activation at the 3-position to generate the intermediate 348 In 2021, Dong and co-workers reported the reaction of (R)-3-formylBINOL-MOM, (R)-241, prepared by the ortho-lithiation of BINOL-MOM followed by reaction with DMF, with pyridine-2-amine (352, 1.5 equiv) and an alkyne (353, 2.5 equiv) catalyzed by [Cp*RhCl 2 ] 2 (Scheme 127). 344 This reaction was carried out in THF at 120 °C by using [Cp*RhCl 2 ] 2 (5 mol %) in the presence of AgNTf (0.2 equiv) and Cu(OAc) 2 •H 2 O (2.0 equiv). It directed a C−H activation at the 4-position of (R)-241 to give the products (R)-354 in up to 94% yields with the retention of the optical purity.…”

Cascade Alkenylation/Intramolecular Friedel–Crafts Alkylation: High Selectivity at the C7-Position of BINOL

“…7-(6′-Fluorospiro[cyclobutane-1,1′-inden]-2′-yl)-6-(1H-pyrazol-1yl)-[1,1′-binaphthalene]-2,2′-diol (3af) 28.8 mg, 55% yield; colorless oil; eluent (PE/ethyl acetate = 3:1). 1 H NMR (600 MHz, DMSO-d 6 ) δ 9.53 (s, 1H), 9.38 (s, 1H), 8.08 (s, 1H), 8.02 (d,J = 8.9 Hz,1H),3H),7.57 (s,1H),7.42 (dd,J = 18.3,9.2 Hz, 2H), 7.28 (d, J = 9.1 Hz, 1H), 7.21 (dd, J = 9.9, 5.6 Hz, 2H), 7.12−6.97 (m, 3H), 6.90 (t, J = 9.0 Hz, 1H), 6.33−6.28 (m, 1H), 6.16 (d, J = 3.0 Hz, 1H), 1.96 (d, J = 9.9 Hz, 1H), 1.86 (m, 3H), 1.70−1.63 (m, 1H), 1.28 (m, 1H). 13 C NMR (100 MHz, CDCl 3 ) δ 160.…”

“…8 Additionally, the rhodium-catalyzed regioselective cascade annulation reaction at the C4-position of BINOL skeletons was disclosed by our group (eq 3). 9 Although such practical approaches have been reported, C−H bond functionalization of other positions of BINOLs remains a pending issue.…”

Three-component acyloxylation of diazo compounds with carboxylic acids and azadienes

“…12 It is widely known that multi-component reactions using diazo compounds have attracted great attention due to their high efficiency and step economy. 13 Despite the important contributions of these studies, a one-pot multi-component study of BDAs has never been reported. Therefore, we envision the discovery of a cascade multi-component reaction of BDAs, diazo compounds and acids to construct complex tertiary alcohol derivatives based on Michael addition (eqn (4)).…”