Direct electrophilic borylation using Y(2)BCl (Y(2) = Cl(2) or o-catecholato) with equimolar AlCl(3) and a tertiary amine has been applied to a wide range of arenes and heteroarenes. In situ functionalization of the ArBCl(2) products is possible with TMS(2)MIDA, to afford bench-stable and easily isolable MIDA-boronates in moderate to good yields. According to a combined experimental and computational study, the borylation of activated arenes at 20 °C proceeds through an S(E)Ar mechanism with borenium cations, [Y(2)B(amine)](+), the key electrophiles. For catecholato-borocations, two amine dependent reaction pathways were identified: (i) With [CatB(NEt(3))](+), an additional base is necessary to accomplish rapid borylation by deprotonation of the borylated arenium cation (σ complex), which otherwise would rather decompose to the starting materials than liberate the free amine to effect deprotonation. Apart from amines, the additional base may also be the arene itself when it is sufficiently basic (e.g., N-Me-indole). (ii) When the amine component of the borocation is less nucleophilic (e.g., 2,6-lutidine), no additional base is required due to more facile amine dissociation from the boron center in the borylated arenium cation intermediate. Borenium cations do not borylate poorly activated arenes (e.g., toluene) even at high temperatures; instead, the key electrophile in this case involves the product from interaction of AlCl(3) with Y(2)BCl. When an extremely bulky amine is used, borylation again does not proceed via a borenium cation; instead, a number of mechanisms are feasible including via a boron electrophile generated by coordination of AlCl(3) to Y(2)BCl, or by initial (heteroarene)AlCl(3) adduct formation followed by deprotonation and transmetalation.
Haloarenes undergo direct borylation using amine : BCl3 : AlCl3 in the ratio of 1 : 1 : 2. After esterification the pinacol boronate esters are isolated in good yield with regioselectivity controlled by steric and electronic effects.
Electron-deficient (n-type) conjugated materials are commonly prepared via step-growth methods with limited control over the molecular weight and molecular weight distribution of the resulting polymers. In this communication, we demonstrate that Pd-dialkylbiarylphosphine catalysts enable the chain-growth polymerization of benzo[1,2,3]triazole using Suzuki-Miyaura coupling with molecular weight control and modest molecular weight distributions (Đ ∼ 1.2−1.6). The importance of a free ligand in the reaction mixture during polymerization was established by analysis of polymer samples using GPC and MALDI-TOF mass spectrometry. A block copolymer with poly(3hexylthiophene) was also synthesized by sequential monomer addition. The success of these commercially available catalysts for polymerization of benzotriazole highlights their potential for chain-growth reactions with other bicyclic arenes in the future.
The synthesis of highly regioregular
poly(3-hexylthiophene-2,5-diyl), rr-P3HT, by Suzuki–Miyaura
polymerization is reported. The key N-methyliminodiacetic
acid (MIDA) boronate ester thienyl monomer was synthesized using a
one-pot multigram scale procedure, in high purity, and in good isolated
yield (80%) by direct electrophilic borylation. Conditions for the
hydrolysis of the MIDA protecting group and the polymerization reaction
were investigated. The optimal procedure gave rr-P3HT with >98%
HT couplings, excellent isolated yields (up to 94%), and polymer molecular
weights up to M
n = 18.7 kDa and M
w = 42.7 kDa. The performance of the MIDA containing
monomer was compared to that of the pinacol boronate ester under identical
polymerization conditions, with the latter producing lower molecular
weight polymers in reduced yield.
Thienyl di-N-methyliminodiacetic acid (MIDA) boronate
esters are readily synthesized by electrophilic C–H borylation
producing bench stable crystalline solids in good yield and excellent
purity. Optimal conditions for the slow release of the boronic acid
using KOH as the base in biphasic THF/water mixtures enables the thienyl
MIDA boronate esters to be extremely effective homo-bifunctionalized
(AA-type) monomers in Suzuki–Miyaura copolymerizations with
dibromo-heteroarenes (BB-type monomers). A single polymerization protocol
is applicable for the formation of five alternating thienyl copolymers
that are (or are close analogues of) state of the art materials used
in organic electronics. The five polymers were produced in excellent
yields and with high molecular weights comparable to those produced
using Stille copolymerization protocols. Therefore, thienyl di-MIDA
boronate esters represent bench stable and low toxicity alternatives
to highly toxic di-trimethylstannyl AA-type monomers that are currently
ubiquitous in the synthesis of these important alternating copolymers.
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