C–H Activation-Based Transformation of Naphthalenes to 3-Iodo-2-naphthylboronic Acid Derivatives for Use in Iterative Coupling Synthesis of Helical Oligo(naphthalene-2,3-diyl)s

Abstract

Oligo(naphthalene-2,3-diyl)s were synthesized by iterative cross-coupling of 1,8-diaminonaphthalene-modified 3-iodo-2-naphthylboronic acids prepared from naphthalenes via Ir-catalyzed C–H borylation, Ru-catalyzed ortho-C–H silylation directed by an anthranilamide-modified boronyl group, and subsequent iododesilylation. The introduction of a chiral diol to the retained terminal boronyl group allowed selective induction of P- or M-helical conformations.

Naphthalene Endoperoxide Heterodimer Designed for Sustained Singlet Oxygen Release

“…The model endoperoxide for 2-aryl substitution 4 was obtained by irradiating a CDCl 3 solution with a red LED array at 630 nm under an oxygen atmosphere. The synthesis for the model endoperoxide for 6-aryl substitution 7 makes use of a very useful regioselective borylation at the 6-position reported by Suginome’s group . Using this method, the borylated compound 5 was obtained at very high yields (up to 98%).…”

“…The synthesis for the model endoperoxide for 6-aryl substitution 7 makes use of a very useful regioselective borylation at the 6-position reported by Suginome's group. 27 Using this method, the borylated compound 5 was obtained at very high yields (up to 98%). Direct coupling of this compound with iodobenzene gives 6phenyl-substituted naphthalene 6, which can be converted to the corresponding endoperoxide 7 under standard photosensitized oxygenation conditions (vide supra).…”

The dioxasilepanyl group as a versatile organometallic unit: studies on stability, reactivity, and utility

“…Because of this contradictory nature, neither stability nor reactivity is perfect. Specifically, it is still difficult to fully avoid undesired degradation of B(pin) units during the transformations of other functional groups, and therefore B(pin) is not desirable as an M. Tougher boron units such as MIDA boronate 3 and B(dan) 4 are known to be tolerant to diverse reaction conditions because of their respective stabilization of the boron centre by intramolecular coordination and electron-donating amino groups. The reactivity of such protected boron units is, in turn, sacrificed and it is usually difficult to directly transform these boron functionalities without deprotection, with the exception of a few cases.…”

Borylation of α,β-Unsaturated Acceptors by Chitosan Composite Film Supported Copper Nanoparticles

“…Delanzomib [ 9 ] and ixazomib [ 10 ] were found to be active in the design of new drugs ( Figure 1 ). On the other hand, organoboron derivatives are important intermediates for various chemical transformations [ 11 , 12 , 13 , 14 , 15 ], such as Suzuki–Miyaura coupling [ 16 , 17 ], Petasis reaction [ 18 ], allylborations [ 19 ], oxidations [ 20 ] and so on. Thus, new methodologies for the synthesis of organoboron compounds were continuously developed by chemists in both laboratories and industry.…”