Silylium ion-mediated cage-opening functionalization of closo-B₁₀H₁₀²⁻ salts

Abstract

The cage-opening functionalization of stable closo-B10H102- salts constitutes a great way to get various boron clusters. However, the known methods to mediate cage-opening functionalization rely on the use of strong...

Decaborane: From Alfred Stock and Rocket Fuel Projects to Nowadays

“…The reaction of decaborane (14) The reactions of Na 2 [closo-B 10 H 10 ] with thiols RSH (R = i-Pr, i-Bu, c-Hx, C 6 H 4 -p-Me, C 6 H 4 -p-F) in hexane in the presence of trimethylsilyl triflate led to the corresponding 6alkyl-and 6-arylsulfides [6-RS-B 10 H 13 ] [205]. It should be noted that the direct reactions of decaborane (14) with alkyl thiols RS lead to its complete degradation to the corresponding trialkylthioborates (RS) 3 B [220].…”

Lewis acid catalyzed Markovnikov hydrobromination and hydrochlorination of alkynes using TMSX (X = Br, Cl)

“…Due to these characteristics, they could be potentially utilized as good hydrohalogenation reagents with good selectivity under mild conditions. 38,39 Herein, we wish to show that with the proper choice of Lewis acids, TMSX (X = Br, Cl) could be employed as efficient hydrobromination and hydrochlorination reagents of terminal alkynes with excellent regioselectivity at room temperature (Scheme 1c).…”

Mn(II)-Catalyzed Markovnikov Hydroiodination of Terminal Aryl Alkynes

“…In 2022, we found that TMSOTf could activate the stable closo-B 12 H 12 2− salt and afforded the ring-opening functionalized product in the presence of nucleophiles (alcohol, thiol). 15 Preliminary mechanistic studies indicated that TMSOTf worked similarly with HOTf, yet with a broader substrate scope due to its milder Lewis acidity. So, we assume that other TMSX reagents could be explored in the classical HX-involved reactions with the help of a catalyst.…”

“…Our group has a special interest in organosilicon chemistry. In 2022, we found that TMSOTf could activate the stable closo -B 12 H 12 2– salt and afforded the ring-opening functionalized product in the presence of nucleophiles (alcohol, thiol) . Preliminary mechanistic studies indicated that TMSOTf worked similarly with HOTf, yet with a broader substrate scope due to its milder Lewis acidity.…”