118513-79-4Relevant articles and documents
Substituent Directed Phototransformations of BN-Heterocycles: Elimination vs Isomerization via Selective B-C Bond Cleavage
Yang, Deng-Tao,Mellerup, Soren K.,Peng, Jin-Bao,Wang, Xiang,Li, Quan-Song,Wang, Suning
, p. 11513 - 11516 (2016)
Electron-rich and -poor BN-heterocycles with benzyl-pyridyl backbones and two bulky aryls on the boron (Ar = tipp, BN-1, Ar = MesF, BN-2) have been found to display distinct molecular transformations upon irradiation by UV light. BN-1 undergoes an efficient photoelimination reaction forming a BN-phenanthrene with PE = 0.25, whereas BN-2 undergoes a thermally reversible, stereoselective, and quantitative isomerization to a dark colored BN-1,3,5-cyclooctatriene (BN-1,3,5-COT, BN-2a). This unusual photoisomerization persists for other BN-heterocycles with electron-deficient aryls such as BN-3 with a benzyl-benzothiazolyl backbone and MesF substituents or BN-4 with a benzyl-pyridyl backbone and two C6F5 groups on the boron. The photoisomerization of BN-4 goes beyond BN-1,3,5-COT (BN-4a), forming a new species (BN-1,3,6-COT, BN-4b) via C-F bond cleavage and [1,3]-F atom sigmatropic migration. Computational studies support that BN-4a is an intermediate in the formation of BN-4b. This work establishes that steric and electronic factors can effectively control the transformations of BN-heterocycles, allowing access to important and previously unknown BN-embedded species.
Traceless Protection for More Broadly Applicable Olefin Metathesis
Mu, Yucheng,Nguyen, Thach T.,van der Mei, Farid W.,Schrock, Richard R.,Hoveyda, Amir H.
supporting information, p. 5365 - 5370 (2019/03/21)
An operationally simple in situ protection/deprotection strategy that significantly expands the scope of kinetically controlled catalytic Z- and E-selective olefin metathesis is introduced. Prior to the addition of a sensitive Mo- or Ru-based complex, treatment of a hydroxy- or a carboxylic-acid-containing olefin with commercially available HB(pin) or readily accessible HB(trip)2 (pin=pinacolato, trip=2,4,6-tri(isopropyl)phenyl) for 15 min is sufficient for efficient generation of a desired product. Routine workup leads to quantitative deprotection. A range of stereochemically defined Z- and E-alkenyl chlorides, bromides, fluorides, and boronates or Z-trifluoromethyl-substituted alkenes with a hydroxy or carboxylic acid group were thus prepared in 51–97 % yield with 93 to >98 % stereoselectivity. We also show that, regardless of whether a polar functional unit is present or not, a small amount of HB(pin) may be used to remove residual water, significantly enhancing efficiency.
