A convenient one-pot synthesis of boroxoles from diboronic acid

Discovery and Characterization of CD12681, a Potent RORγ Inverse Agonist, Preclinical Candidate for the Topical Treatment of Psoriasis

“…Benzoboroxoles have recently been added to the medicinal chemist's arsenal, and specifically in dermatology, with the approval of crisaborole in 2016 for the topical treatment of atopic dermatitis. In this case, N ‐(4‐ethylphenyl)‐1‐hydroxy‐ N ‐isobutyl‐3‐[(tetrahydro‐2 H ‐pyran‐4‐yl)methyl]‐1,3‐dihydrobenzo[ c ][1,2]oxaborole‐6‐sulfonamide ( 10 q ) showed comparable activity with slightly reduced lipophilicity versus indazole 4 a , and did not warrant further investigation at this stage …”

“…In this case, N-(4-ethylphenyl)-1-hydroxy-Nisobutyl-3-[(tetrahydro-2H-pyran-4-yl)methyl]-1,3-dihydrobenzo[c][1,2]oxaborole-6-sulfonamide (10 q)s howed comparable activity with slightly reduced lipophilicityv ersus indazole 4a, and did not warrant further investigation at this stage. [29] An investigation of 6,6-bicyclic systems was then started. 1,2,3,4-Tetrahydroquinoxaline derivative 11 a offered an encouraging startingp oint, highlighting again the key hydrogenbond donor meta to the sulfonamide group.…”

Modular Synthesis of Complex Benzoxaboraheterocycles through Chelation-Assisted Rh-Catalyzed [2 + 2 + 2] Cycloaddition

“…70−73 Due to the sensitivity of the cycloaddition toward sterics, substitution on the diyne (31) and at the propargylic position (32−34) was not well tolerated. 58 The remaining monoalkynes were poorly reactive overall in the [2 + 2 + 2] cycloaddition (35,36).…”

“…Classical approaches to the BOB framework have been based on nucleophilic addition of stoichiometric organometallics to a borylated arene bearing an adjacent carbonyl or borylation of an ortho -halo benzyl alcohol derivative using Miyaura-type conditions (Scheme a). − Contemporary approaches include B-insertion strategies using B–Br reagents (Scheme b), such as a dual Ni/Zn catalysis to insert a boron unit into the C­(sp 3 )–O bond of benzodihydrofurans by Dong and co-workers and the electrophilic haloboration approach reported by Ingleson and co-workers to directly access benzoxaboronines from o -alkynyl phenols . A complementary approach that does not rely upon electrophilic borylating agents or C–B bond formation was developed by Sheppard and co-workers, where gold catalysis generated the benzoxaborinine from o -alkynyl boronic acids …”

Modular synthesis of complex benzoxaboraheterocycles through chelation-assisted Rh-catalyzed [2+2+2]cycloaddition

“…Classical approaches to the BOB framework have been based on nucleophilic addition of stoichiometric organometallics to a borylated arene bearing an adjacent carbonyl, 34 or borylation of an ortho-halo benzyl alcohol derivative using Miyaura-type conditions (Scheme 1a). [35][36][37] Con-temporary approaches include B-insertion strategies using B-Br reagents (Scheme 1b), such as a dual Ni/Zn catalysis to insert a boron unit into the C(sp 3 )-O bond of benzodihydrofurans by Dong and coworkers, 38 and the electrophilic haloboration approach reported by Ingleson and coworkers to directly access benzoxaboronines from oalkynyl phenols. 39 A complementary approach that does not rely upon electrophilic borylating agents or C-B bond formation was developed by Sheppard and coworkers, where gold catalysis generated the benzoxaborinine from o-alkynyl boronic acids.…”