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Pd-catalyzed β-carbon elimination of 3-hydroxy-4-pent­enoic acid derivatives promoted by triethylborane proceeds to form conjugated dienes via a decarboxylation process. The formed conjugated dienes undergo the Prins reaction with aldehydes in situ to afford conjugated homoallylic alcohols. These sequential transformations enable the conversion of diastereomeric mixtures of 3-hydroxy-4-pentenoic acids, which are readily prepared from the simple crossed aldol reaction of esters and α,β-unsaturated aldehydes, into 3,5-hexadienyl alcohols with high regio- and stereoselectivities in a single manipulation.

Poly(ester-carbonate) copolymers were synthesized through triethylborane (TEB)-activated, one-pot copolymerization of epoxides with anhydrides (AH) and CO₂. Depending upon the feeding ratio of AH to the epoxides, poly(ester-carbonate) copolymers with random and tapered ester structures could be derived due to the much higher reactivity of AH toward growing oxanions compared to the reactivity of CO₂. Anhydrides like succinic anhydride (SA) and phthalic anhydride (PA) when tried in terpolymerization with epoxides, like propylene oxide (PO) and cyclohexene oxide (CHO), and CO₂ indeed exhibited such high reactivities in comparison to CO₂ that tapered block structures were eventually obtained for high feeding ratios of AH to PO and random copolymers for the AH-to-epoxide feeding ratio lower than 10%. Terpolymerization with different feeding ratios of anhydrides to epoxides was thus systematically investigated. In an alternate path, diblock poly(ester-b-carbonate)s were prepared by sequential copolymerization of epoxide/anhydride and epoxide/CO₂. All of the obtained copolymers were characterized by ¹H nuclear magnetic resonance (NMR), diffusion-ordered spectroscopy (DOSY), gel permeation chromatography (GPC), and differential scanning calorimetry (DSC). The structures and properties of copolymers obtained by terpolymerizations and block copolymerizations were compared.

The first C5 polymerization is reported, where the main‐chain is growing by five carbon atoms of the monomer at a time. Three dienyltriphenylarsonium ylide monomers were synthesized and polymerized with triethylborane as an initiator, leading to random terpolymers (C1, C3, C5) with mainly C5 repeating units (up to 84.1 %). It has been found that the methyl group (electron‐donating substituent) on the conjugated double bond of the ylides facilitates the formation of C5 segments. A mechanism was proposed based on NMR characterization and DFT calculations. The high C5 content ensures that things are on the right track for pure C5 homopolymerization., Reported for the first time is an unusual borane‐initiated polymerization of arsonium ylide monomers, where the main‐chain grows by five carbon atoms, from the monomer, at a time and leads to unique structures.

Biomass-derived 5-chloromethylfurfural (CMF), a congener of the well-known carbohydrate-based platform chemical 5-hydroxymethylfurfural (HMF), can efficiently be functionalised by radical transformations of its benzylic chloromethyl group. We report here the first examples of these radical reactions by way of metal-free, triethylborane/oxygen-induced atom transfer radical addition (ATRA) reactions between CMF and styrenes, which proceed with high yield and selectivity. The key intermediate, the 2-formyl-5-furfuryl radical derived from CMF, and its radical addition reactions were studied with regard to its electronic structure, i.e. spin density distribution and frontier molecular orbitals based on the NBO ansatz and activation barriers of the addition step using DFT and post-HF methods.

The activation and deactivation of the chain-transfer agent were achieved by oxygen initiation and regulation with triethylborane under ambient temperature and atmosphere. The autoxidation of triethylborane overcame the oxygen inhibition and produced initiating radicals that selectively activate the chain-transfer agent for the chain growth or deactivate the active chain-end of polymer in controlled radical polymerization. Both activation and deactivation were highly efficient with broad scope for various polymers with different chain-transfer agents in both organic and aqueous systems. Oxygen molecule was particularly used as an external regulator to initiate and achieve the temporal control of both activation and deactivation by simply feeding the air.

A key challenge in polymer chemistry is to regulate the polymer sequence and architecture from versatile monomer mixtures. Here we describe the triethylborane/1,8-diazabicyclo[5.4.0]undec-7-ene (Et3B/DBU) pair catalysed highly selective terpolymerization of mixtures of propylene oxide (PO), phthalic anhydride (PA) and racemic lactide (rac-LA), wherein the catalytic efficiency and the polymerization selectivity are significantly correlated to the Et3B/DBU feed ratio. With H2O as a cheap and efficient initiator, the Et3B/DBU pair (1/1) demonstrates chemoselective control over the ring-opening copolymerization (ROCOP) of PO/PA and the ring-opening polymerization (ROP) of rac-LA, while the Et3B/DBU pair (2/1) additionally allows for the discrimination of rac-LA and PO in ROP via kinetic control, affording one-step access to unique AzCy(AB)xCyAz pentablock terpolymers (Đ < 1.15) without transesterification scrambling.

In this paper, the DFT methods were applied at the M06-2X/6–311++G(d,p) levels of theory to investigate the β-hydrogen elimination in the (C2X5)2B(C2H5); X=H, F, Cl, Br. It was attempted to show how the electronegativity of halogen affects the barrier height (ΔE‡) and thermodynamic parameters (ΔG‡ and ΔH‡) of this reaction. The Wiberg bond indices were employed to check the progress of the reactions. The synchronicity values of the reactions were determined as well. The kinetic parameters of these reactions were computed in 300-1200 K temperature range. Furthermore, the fitted equations to the gas phase Arrhenius equation were found. Effect of the electronegativity of halogen was exemplified on the kinetic parameters.

Pd-catalyzed regio- and enantioselective allylic etherification of vinylethylene carbonates (VECs) with diols has been developed. By using cooperative catalysts of the chiral palladium complex and triethylborane in mild conditions, the process gave monoetherified and bisetherified polyglycol derivatives with tetrasubstituted stereocenters in high yields with complete regioselectivities and high levels of enantio- and diastereoselectivities.

A general method for the hydroalkylation of electron-rich terminal and non-terminal alkenes such as enol esters, alkenyl sulfides, enol ethers, silyl enol ethers, enamides and enecarbamates has been developed. The reactions are carried out at room temperature under air initiation in the presence of triethylborane acting as a chain transfer reagent and 4-tert-butylcatechol (TBC) as a source of hydrogen atom. The efficacy of the reaction is best explained by very favorable polar effects supporting the chain process and minimizing undesired polar reactions. The stereoselective hydroalkylation of chiral N-(alk-1-en-1-yl)oxazolidin-2-ones takes place with good to excellent diastereocontrol., Giese reaction not anymore limited to electron poor alkenes! A general method for the radical mediated hydroalkylation of electron rich alkenes including enol ethers, silylenolethers, enamides, and enecarbamates has been developed.

Phthalic anhydride and propylene/ethylene oxide are copolymerized at room temperature by a bicomponent metal-free catalyst comprising a mild phosphazene base and triethylborane. Provided with proper loadings of the two catalytic components, block copolymers with strict (AB)

Synthesis of high molecular weight alternating copolymers from epoxides and norbornene anhydride via metal-free catalyst remains a challenge in aliphatic biodegradable polyester synthesis. Metal-free Lewis pair catalyst system, consisting of Lewis acid B(C2H5)3 (triethylborane) and a Lewis base DMAP (4-dimethylaminopyridine); TBD (1, 5, 7-triazabicyclo[4.4.0]dec-5-ene) and DBU (1,8 diazabicyclo[5.4.0]undec-7-ene) as a cooperative catalyst system for fully alternating polyesters synthesis is described here. By using these simple systems we have obtained, high molecular weight (Mn = 2–31.5 kDa) polyesters with narrow molecular weight distributions (MWD’s = 1.948–1.069) via ring-opening alternating copolymerisation (ROAC) of various epoxides (e.g. CHO, cyclohexene oxide; PO, propylene oxide; tBGE, tert-butyl glycidyl ether and PGE, phenyl glycidyl ether) with cis-5 norbornene-endo 2, 3 dicarboxylic anhydride (NB). Furthermore, we demonstrated that these polyesters are biocompatible in nature when tested on human embryonic kidney cells (HEK-293) showing more than 80% cell viability in 72 h and can be used for different biological applications such as drug delivery, tissue engineering or anti-microbial polymeric coatings on biomedical devices. The use of these green functional polyesters for biological studies was realized for the first time by a metal-free Lewis pair approach.

Reported herein is the development of a simple but practical catalytic system for the selective reduction of amides with hydrosilane or hydrosiloxane. Low-cost and readily available triethylborane (1.0 M in THF), in combination with a catalytic amount of an alkali metal base, was found to catalyze the reduction of all three amide classes (tertiary, secondary, and primary amides) to form amines under mild conditions. In addition, the selective transformation of secondary amides to aldimines and primary amides to nitriles can also be achieved by using a proper combination of BEt3 and base. The scope of these BEt3-base-catalyzed amide hydrosilylation reactions has been explored in depth. Preliminary results of mechanistic studies suggest a modified Piers' silane Si-H···B activation mode wherein the hydride abstraction by BEt3 is promoted by the coordination of an alkoxide or hydroxide anion to the Si center.

Tetrabutylammonium carbonate (TBAC) which is obtained by treating CO2 with tetrabutylammonium hydroxide is shown to perform as an ideal difunctional initiator for the copolymerization of carbon dioxide (CO2) and propylene oxide (PO) in the presence of triethylborane (TEB). In this system, CO2 thus serves as the initiating moiety of its own copolymerization with epoxides when used in the form of a carbonate salt. Based on this remarkable result, mono-, tri-, and tetrafunctional ammonium carboxylate initiators and also other difunctional carboxylate initiators were synthesized and used for the synthesis of well-defined ω-hydroxyl-polycarbonates with linear and star structures. Well-defined telechelics, three- and four-armed star samples of molar mass varying from 1 kg/mol to 10 kg/mol, with around 95% carbonate content, were successfully synthesized. The structure of the obtained polycarbonate ω-polyols were characterized by 1H NMR, MALDI-TOF, and GPC. The terminal hydroxyl functionality of polycarbonate di...

An efficient method for the construction of arylated allylic ethers was developed via three-component tandem arylation and allylic etherification of 2,3-allenol with aryl iodides and alcohols. In the cooperative catalytic system of a palladium complex and triethylborane, the process allows rapid access to functionalized 1-arylvinylated 1,2-diol derivatives in good to high yields with complete branch-selectivities. The synthetic utility of the present process was demonstrated by the late-stage functionalization of a drug molecule, the gram-scale synthesis and the elaboration of the products.

Various oxirane monomers including alkyl ether or allyl-substituted ones such as 1-butene oxide, 1-hexene oxide, 1-octene oxide, butyl glycidyl ether, allyl glycidyl ether, and 2-ethylhexyl glycidyl ether were anionically copolymerized with CO2 into polycarbonates using onium salts as initiator in the presence of triethylborane. All copolymerizations exhibited a "living" character, and the monomer consumption was monitored by in situ Fourier-transform infrared spectroscopy. The various polycarbonate samples obtained were characterized by H-1 NMR, GPC, and differential scanning calorimetry. In a second step, all-polycarbonate triblock copolymers demonstrating elastomeric behavior were obtained in one pot by sequential copolymerization of CO2 with two different epoxides, using a difunctional initiator. 1-Octene oxide was first copolymerized with CO2 to form the central soft poly(octene carbonate) block which was flanked by two external rigid poly(cyclohexene carbonate) blocks obtained through subsequent copolymerization of cyclohexene oxide with CO2. Upon varying the ratio of 1-octene oxide to cyclohexene oxide and their respective ratios to the initiator, three all-polycarbonate triblock samples were prepared with molar masses of about 350 kg/mol and 22, 26, and 29 mol % hard block content, respectively. The resulting triblock copolymers were analyzed using H-1 NMR, GPC, thermogravimetric analysis, differential scanning calorimetry, and atomic force microscopy. All three samples demonstrated typical elastomeric behavior characterized by a high elongation at break and ultimate tensile strength in the same range as those of other natural and synthetic rubbers, in particular those used in applications such as tissue engineering.

In this investigation, a metal-free process was developed that enables the synthesis of poly(propylene carbonate) (PPC) diols/polyols by copolymerization of CO2 with propylene epoxide (PO) under environmentally friendly and cost-effective conditions. This process implies the recycling of triethylborane and of ammonium salts that both enter in the composition of the initiators used to copolymerize CO2 and PO. In complement to the above approach, a polymeric support, poly(diallyl dimethylammonium chloride), was synthesized and modified to carry ammonium carboxylate salts along its chain. The prepared polymeric initiator was utilized to copolymerize CO2 with PO under heterogeneous conditions. Not only were the polymerization results similar to the samples obtained under homogeneous conditions, but the polymer substrate could easily be recovered by simple filtration. The integrity of the polycarbonate diols/polyols and the recycling process were followed by 1 H and 11 B NMR spectroscopy, gel permeation chromatography, and matrix assisted laser desorption ionization time of flight (MALDI-TOF) MS.

The heats of combustion at 25 °C of trimethylborane (liquid), triethylborane (liquid), and tri-n-butylborane (liquid), to form crystalline boric acid, liquid water, and gaseous carbon dioxide have been determined to be −2989.4 ±22.4 kj/mole (−714.48 ±5.36 kcal/mole), −4975.6 ±15.1 kj/mole (−1189.2 ±3.6 kcal/mole), and −8901.0 ±10.2 kj/mole (−2127.4 ±2.4 kcal/mole), respectively. These data, combined with the heats of formation of boric acid, carbon dioxide, and water give −34.79 ±5.40, −47.2 ±3.7, and −83.2 ±2.5 kcal/mole at 25 °C for the standard heats of formation of trimethylborane, triethylborane, and tri-n-butylborane, respectively. The data of other investigators are discussed briefly.

Пегеев Никита Леонидович – аспирант химического факультета, Нижегородский государственный университет им. Н.И. Лобачевского. 603950, г. Нижний Новгород, пр. Гагарина, 23. E-mail: nikita.pegeev@mail.ru Маткивская Юлия Олеговна – младший научный сотрудник лаборатории нефтехимии НИИ химии, Нижегородский государственный университет им. Н.И. Лобачевского. 603950, г. Нижний Новгород, пр. Гагарина, 23. E-mail: yulia-univer@mail.ru Валетова Наталья Борисовна – кандидат химических наук, старший научный сотрудник лаборатории нефтехимии НИИ химии, Нижегородский государственный университет им. Н.И. Лобачевского, Россия, 603950, г. Нижний Новгород, пр. Гагарина, 23. E-mail: nata-bor- 2005@mail.ru Митин Александр Вячеславович – кандидат химических наук, старший научный сотрудник, руководитель Центра коллективного пользования НИИ химии, Нижегородский государственный университет им. Н.И. Лобачевского. 603950, г. Нижний Новгород, пр. Гагарина, 23. E-mail: ckp@ichem.unn.ru Лиогонькая Татьяна Израилевна – ведущий инженер кафедры химии нефти (нефтехимического синтеза), Нижегородский государственный университет им. Н.И. Лобачевского. 603950, г. Нижний Новгород, пр. Гагарина, 23. E-mail: senft@yandex.ru Семенычева Людмила Леонидовна – доктор химических наук, доцент, зав. лабораторией нефтехимии НИИ химии, Нижегородский государственный университет им. Н.И. Лобачевского. 603950, г. Нижний Новгород, пр. Гагарина, 23. E-mail: llsem@yandex.ru. N.L. Pegeev, nikita.pegeev@mail.ru Yu.O. Matkivskaya, yulia-univer@mail.ru N.B. Valetova, nata-bor-2005@mail.ru A.V. Mitin, ckp@ichem.unn.ru T.I. Liogonkaya, senft@yandex.ru L.L. Semenycheva, llsem@yandex.ru Lobachevsky State University of Nizhni Novgorod, Nizhny Novgorod, Russian Federation Синтез сополимеров бутилакрилата с винилизобутиловым эфиром осуществляли путем добавления активного мономера в избыток сомономера при его кипении в присутствии триэтилборана. Элементоорганический соинициатор выделяли из комплекса с гексаметилендиамином в растворе винилизобутилового эфира, добавляя метакриловую кислоту в количестве, пропорциональном в молях количеству амина, вместе с бутилакрилатом. В качестве соинициатора к триэтилбору выступает кислород воздуха, присутствующий в незначительных количествах в реакционной смеси при кипении эфира. Введение бутилакрилата осуществлено в течение 20 мин. После этого процесс останавливали (в первой серии образцов), или реакционную смесь термостатировали еще в течение 20 мин (во второй серии образцов). По окончании полимеризации жидкую фракцию отгоняли. Образцы сополимеров выделяли удалением мономеров в вакууме, их конверсию оценивали по сухому остатку гравиметрически. Молекулярно-массовые параметры для образцов определены методом гель-проникающей хроматографии. Состав сополимеров определяли методом ИК-спектроскопии с применением градуировочного графика по площади характеристического пика. Полученные данные дают основание предположить, что при сополимеризации бутилакрилата с винилизобутиловым эфиром имеет место образование макромолекулярной цепи по двум центрам: олигомерному и низкомолекулярному. Образование олигомера наряду с низкомолекулярным полимером, обычно формирующимся в таких условиях при традиционном радикальном инициировании, объясняется присутствием в реакционной смеси бороксильного радикала, который известен при окислении триалкилборанов. За счет взаимодействия последнего с инициирующими R• или RO• радикалами, которые также зафиксированы при окислении триалкилборанов, или олигомерными растущими радикалами формируется центр роста полимерной цепи по механизму обратимого ингибирования с очень низкой степенью полимеризации. Продолжение термостатирования реакционной смеси после дозирования бутилакрилата с метакриловой кислотой приводит к смещению олигомерной моды в сторону увеличения значения молекулярной массы, соответственно увеличивается Мn и уменьшается Mw/Mn. Это происходит за счет того, что процесс сополимеризации продолжается в отсутствии инициатора за счет реакции обратимого ингибирования. Зависимость конверсии от времени характеризуется резким уменьшением скорости на конверсии 40–60 %, что также связано с переходом способа формирования макромолекул с преимущественно за счет бимолекулярного обрыва с высокой скоростью к процессу по механизму обратимого ингибирования, который проходит со значительно меньшей скоростью. Состав сополимеров характеризуется чуть большим эквимольного содержанием акрилата, что связано с большим значением относительной активности винилизобутилового эфира, в паре с бутилакрилатом при сополимеризации (rВБЭ ≈ 0; rБА = 5,2 ± 1,5; rВиБЭ ≈ 0). The synthesis of copolymers of butyl acrylate with vinyl isobutyl ether was carried out by adding the active monomer to the excess of the comonomer when boiling in the presence of triethylborane. An organoelement co-initiator was isolated from a complex with hexamethylenediamine in a solution of vinyl butyl ether, with addition of methacrylic acid in an amount proportional to the amount of amine in moles, together with butyl acrylate. As a coinitiator of triethylborane, air oxygen was present in the reaction mixture at boiling of the vinyl butyl ether. The introduction of butyl acrylate was completed within 20 minutes. After that, the process was stopped (in the first series of samples), or else the reaction mixture was thermostated for another 40 minutes (in the second series of samples). At the end of polymerization, the liquid fraction was distilled off. The copolymer samples were isolated by removing the monomers under vacuum, and their conversion was evaluated gravimetrically by the dry residue. Molecular weight parameters for the samples were determined by gel permeation chromatography. The composition of the copolymers was determined by IR spectroscopy using a calibration graph based on the area of the characteristic peak. The obtained data suggest that during the copolymerization of butyl acrylate with vinyl isobutyl ether, a macromolecular chain is formed along two centers: oligomeric and low-molecular. The formation of an oligomer along with a low-molecular polymer, usually formed under such conditions at traditional radical initiation, is explained by the presence of boroxyl radicals in the reaction mixture, which are known in the oxidation of trialkylboranes. Due to the interaction of the latter with initiating R• or RO• radicals, which are also observed during the oxidation of trialkylboranes, or with oligomeric growing radicals, a growth center of the polymer chain is formed by the mechanism of reversible inhibition with a very low degree of polymerization. Continued thermostating of the reaction mixture after dosing butyl acrylate with methacrylic acid leads to a shift in the oligomeric mode in the direction of increasing the value of molecular weight; accordingly, Mn increases and Mw/Mn decreases. This occurs because the copolymerization process continues in the absence of the initiator due to the reversible inhibition reaction. The time-dependent conversion rate is characterized by an abrupt decrease in the conversion rate by 40–60 %, which is also associated with the transition of the method of forming macromolecules with the predominantly high-speed bimolecular break to a process following the reversible inhibition mechanism according to the scheme, which runs at a much lower rate. The composition of the copolymers is characterized by a slightly higher equimolar content of acrylate, with a higher value of the relative activity of vinyl isobutyl ether, paired with butyl acrylate during copolymerization (rBA = 1.45 ± 0.07; rVBE ≈ 0; rBA = 5.2 ± 1.5; rViBE ≈ 0). Работа выполнена с использованием оборудования ЦКП «Новые материалы и ресурсосберегающие технологии» НИИХ ННГУ.

International audience; Propylene oxide (PO) is polymerized by metal-free ring-opening 11 polymerization (ROP) at 25 °C using N-heterocyclic carbenes (NHCs) and 12 triethylborane (Et 3 B) as a bicomponent catalytic system. Poly(propylene oxide)s with 13 predictable molar mass up to 60 000 g.mol-1 and low dispersity (Ð < 1.10) were 14 obtained without the occurrence of undesirable transfer reaction to the monomer. In 15 presence of an alcohol as the initiator, the ROP of PO follows an anionic mechanism 16 assisted by monomer activation improving the efficiency of NHCs for the 17 polymerization of substituted epoxides. Et 3 B is involved both in the formation of a 18 complexed active center and in the activation of PO. Interestingly, 19 dihydroxytelechelic PPOs can be readily synthesized not only using 1,4-20 benzenedimethanol but also water, both serving as difunctional initiators. Block

Ring-opening polymerization (ROP) is a versatile approach to well-defined polymers. Achieving both high efficiency and precise control remains a major challenge. We herein report room-temperature living ROP of epoxides catalyzed by combined organobase and triethylborane (Et3B) with water or alcohols as initiators. Extremely high catalytic efficiency (turnover frequency up to 6000 h–1) is exhibited despite the relatively mild Lewis basicity and acidity, and the catalyst loading can be minimized to 44 ppm. Poly(ethylene oxide) products are noncytotoxic toward a variety of cell lines even without purification. Poly(propylene oxide) with molar mass as high as 210 kg mol–1 and low dispersity (ĐM < 1.1) can be achieved owing to the absence of detrimental transfer reactions. The chemoselectivity allows the catalyst to be readily applied to living ROP of glycidyl ethers, tailored synthesis of diverse functional/block/nonlinear (co)polyether structures, and one-pot one-catalyst synthesis of polyether-based polyure...

A series of aggregation-induced emission (AIE) active core crosslinked miktoarm star copolymers, having multi polyethylene (PE) and poly(methacrylic acid) (PMAA) arms, were synthesized and their thermal/pH responsive properties were studied. The procedure involves (a) the synthesis of PE-Br by polyhomologation of dimethylsulfoxonium methylide with triethylborane as initiator, followed by oxidation-hydrolysis/esterification reactions and of poly(tert-butyl methacrylate) (PtBMA-Br) by atom transfer radical polymerization (ATRP) of tert-butyl methacrylate, (b) the synthesis of (PE)n-(PtBMA)m-P(TPE-2St) by ATRP of a double styrene-functionalized tetraphenylethene (TPE-2St) with PE-Br and PtBMA-Br macroinitiators, and (c) the hydrolysis of (PE)n-(PtBMA)m-P(TPE-2St) to afford the amphiphilic miktoarm star copolymers (PE)n-(PMMA)m-P(TPE-2St). Due to their spherical core–shell structure (temperature-responsive) and the presence of hydrophilic PMAA (pH-responsive) and TPE-2St (AIE), these miktoarm star copolymers ...

A rapid oxygen-initiated and -regulated controlled radical polymerization was conducted under ambient temperature and atmosphere. The reaction between triethylborane and oxygen provides ethyl radicals, which initiate and mediate the radical polymerization. The controlled radical polymerization was achieved using RAFT chain transfer agents (CTA) without any process of removing oxygen, providing well-defined polymers with almost full conversion (>95 %) in a short period (15 min). High-throughput screening was used to discover the suitable conditions for various CTA and monomers. To show the versatility of this method, a polymer library containing 25 well-defined polymers with different compositions (block and statistical copolymers) and molecular weights were synthesized in 1 h via high-throughput synthesis technique. A polymer-painting technique was developed using this method, forming films with spatial control and excellent control in molecular weight and dispersity.

The C≡C bonds of various alkynylgermanes [Cl(H)Ge(C≡C–R1)2, Cl2Ge(C≡C–R1)2 with R1 = nBu, SiMe3, and Ge(C≡C–R1)4 with R1 = SiMe3] undergo 1,1-carboboration when treated with an excess of triethylborane at 80–110 °C. All pure final products with R1 = SiMe3 possess germole-derived structures. Intermediates and side products as a result of lost stereoselectivity of the 1,1-carboborations could be detected and in some cases identified by NMR spectroscopic studies of the reaction solutions.

A radical "on water" addition to the C═N bond of hydrazones has been described. Hydrazone, diphenylsilane, alkyl iodide, and triethylborane afforded the corresponding addition products "on water" in good yields. A significant solvent effect was observed from the water. The developed protocol can be applied to the synthesis of 3-substituted isoindolinone derivatives. Moreover, the process offers environmentally benign tin-free radical reaction conditions.

Selective incorporation of deuterium atoms into molecules is of high interest for labeling purposes and for optimizing properties of drug candidates. A mild and environmentally benign method for the deuteration of alkyl iodides via radical pathway using D2O as source of deuterium has been developed. The reaction is initiated and mediated by triethylborane in the presence of dodecanethiol as a catalyst. This method is compatible with a wide range of functional groups and provides the monodeuterated products in good yields and with a high level of deuterium incorporation. It opens promising opportunities for the development of enantioselective radical reactions. Moreover, a revision of the mechanism of the deoxygenation reaction of xanthates using R3B and water (Wood deoxygenation) is presented.