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Synthesis of alkylboronic acids and alkylboronates

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A mild Pd-catalyzed process for the borylation of primary alkyl bromides using bis(pinacolato)diboron as a boron source tolerates a wide range of functional groups on the alkyl bromide substrate and offers complete selectivity in the presence of a secondary bromide. This approach has been extended to the use of alkyl iodides and alkyl tosylates, as well as borylation reactions employing bis(neopentyl glycolato)diboron as the boron source.
A. Joshi-Pangu, X. Ma, M. Diane, S. Iqbal, R. J. Kribs, R. Huang, C.-Y. Wang, M. R. Biscoe, J. Org. Chem., 2012, 77, 6629-6633.

CeO₂ nanorods catalyze the borylation of alkyl halides and aryl iodides with B₂pin₂. A wide range of synthetically useful boronate esters are readily obtained demonstrating broad utility and functional group tolerance. The catalyst can be reused for up to six runs without appreciable loss in activity.
R. Bhawar, S. Saini, K. S. Patil, D. H. Nagaraju, S. K. Bose, J. Org. Chem., 2023, 88, 16270-16279.

Very low amounts of Manganese(II) bromide and tetramethylethylenediamine (TMEDA) catalyze the cross coupling of (bis)pinacolatodiboron with a wide range of alkyl halides. This method allows access to primary, secondary, and tertiary boronic esters.
T. C. Atack, S. P. Cook, J. Am. Chem. Soc., 2016, 138, 6139-6142.

The use of low-cost iron(III) acetoacetate and tetramethylethylenediamine (TMEDA) enables a mild direct cross-coupling of alkyl halides with bis(pinacolato)diboron at room temperature. Moreover, the borylation of benzylic or allylic chlorides, tosylates, and mesylates is possible. The reactions show broad functional-group compatibility.
T. C. Atack, R. M. Lecker, S. P. Cook, J. Am. Chem. Soc., 2014, 136, 9521-9523.

Electroreduction at a high current enables a fast, scalable, and transition-metal-free borylation of alkyl halides (X = I, Br, Cl) at room temperature. This process provides an efficient and practical access to primary, secondary, and tertiary boronic esters, including late-stage borylation of natural products and drug derivatives.
B. Wang, P. Peng, W. Ma, Z. Liu, C. Huang, Y. Cao, P. Hu, X. Qi, Q. Lu, J. Am. Chem. Soc., 2021, 143, 12985-12991.

A catalyst formed in situ from NiBr₂ • diglyme and a pybox ligand accomplishes Miyaura-type borylations of unactivated tertiary, secondary, and primary alkyl halides with diboron reagents to furnish alkylboronates. The method exhibits good functional-group compatibility and is regiospecific.
A. S. Dudnik, G. C. Fu, J. Am. Chem. Soc., 2012, 134, 10693-10697.

The formation of electron-donor-acceptor complexes between N-alkylpyridinium salts and bis(catecholato)diboron enables photoinduced single-electron transfer and fragmentation to carbon-centered radicals, which are subsequently borylated. This mild and operationally simple deaminative borylation allow a diverse range of readily available alkylamines to be efficiently converted into synthetically valuable alkylboronic esters under catalyst-free conditions.
J. Wu, L. He, A. Noble, V. K. Aggarwal, J. Am. Chem. Soc., 2018, 140, 10700-10704.

A decarboxylative borylation of m-chloroperoxybenzoic acid activated fatty acids with bis(catecholato)diboron in N,N-dimethylformamide provides a variety of alkylboronates at room temperature.
D. Wei, T.-M. Liu, B. Zhou, B. Han, Org. Lett., 2020, 22, 234-238.

Visible-light mediates a photochemical conversion of redox-active esters of primary, secondary, and tertiary alkylcarboxylic acids with hypoboric acid into the corresponding boronic esters. Quantum chemical calculations and mechanistic considerations provide deeper insights into the mechanism of photochemical borylation reactions.
B. Nagy, Z. Gonda, T. Földesi, P. P. Fehér, A. Stirlig, G. L. Tolnai, Z. Novák, Org. Lett., 2024, 26, 2292-2296.

An operationally simple decarboxylative borylation reaction of readily available aliphatic acid derivatives under additive-free visible-light photoredox conditions provides primary and secondary alkyl boronates or tetrafluoroborates with various functional groups. A catalytic cycle involving alkyl radical reaction with base-activated diboron species has been proposed.
D. Hu, L. Wang, P. Li, Org. Lett., 2017, 19, 2770-2773.

An efficient visible-light-induced decarboxylative borylation of α- and β-amino redox-active esters with bis(catecholato)diboron, followed by transamination with 1,8-diaminonapthalene (DANH₂) provide a series of boronamides in good yields in a one-pot procedure. The photochemical can also be conducted under flow conditions.
A. Serafino, H. Pierre, F. Le Vaillant, J. Boutet, G. Guillamot, L. Neuville., G. Masson, Org. Lett., 2023, 25, 9249-9254.

Supported gold catalysts efficiently promote the borylation of stable C(sp³)-O bonds of alkyl esters. The use of a disilane as an electron source and gold nanoparticles as a single-electron transfer catalyst is the key to generating alkyl radicals. A subsequent cross-coupling with bis(pinacolato)diboron affords the desired alkyl boronates.
M. Doi, H. Miura, T. Shishido, Org. Lett., 2024, 26, 2902-2907.

Cu-catalyzed formal hydroboration of terminal or 1,1-disubstituted alkenes with bis(pinacolato)diboron and methanol provides products with exceptional regiocontrol favoring the branched isomer. Subsequent photocatalytic cross-couplings using iridium and nickel cocatalysis enable a highly regioselective hydroarylation of terminal alkenes.
H. A. Kerchner, J. Montgomery, Org. Lett., 2016, 18, 5760-5763.

An asymmetric nickel-catalyzed borylative coupling of terminal alkenes with nonactivated alkyl halides provides a broad range of chiral boronic esters with high regio- and enantioselectivity under mild reaction conditions. The success of this three-component strategy is ascribed to the application of a chiral anionic bisoxazoline ligand.
Z. Li, H. Shi, X. Chen, L. Peng, Y. Li, G. Yin, J. Am. Chem. Soc., 2023, 145, 13603-13614.

AgOAc catalyzes an anti-Markovnikov hydroboration of alkenes, 1,3-dienes, and alkynes with pinacolborane (HBpin). This strategy provides an various alkyl-, allyl-, and (E)-alkenylboronate esters regio- and stereoselectively in very good yields under ligand- and base-free conditions.
Y. Wang, R. Guan, P. Sivaguru, X. Cong, X. Bi, Org. Lett., 2019, 21, 4035-4038.

The use of hexamethyldisilazane lithium as a precatalyst enables a lithium-promoted hydroboration of alkynes and alkenes with HBpin as the hydride source. This method offers a remarkable substrate tolerance and good yields. The hydroboration proceeds through in situ-formed BH₃ driving the turnover of the hydroboration of alkynes and alkenes.
J. Liu, C. Wu, T. Hu, W. Yang, Y. Xie, Y. Shi, Q. Li, Y. Shao, F. Zhang, J. Org. Chem., 2022, 87, 3442-3452.

Simple, commercially available borane adducts, H₃B·THF and H₃B·SMe₂ catalyse a highly regioselective hydroboration of terminal alkynes and alkenes with pinacolborane to give linear boronic esters. The reaction tolerates ester, amine, ether and halide substituents. This catalytic process shows comparable reactivity to transition-metal-catalysed hydroboration protocols.
N. W. J. Ang, C. S. Buettner, S. Docherty, A. Bismuto, J. R. Carney, J. H. Docherty, M. J. Cowley, S. P. Thomas, Synthesis, 2018, 50, 803-808.

Counterion dissociation enabled earth-abundant metal catalysis of alkene hydroboration. Commercially available iron and cobalt tetrafluoroborate salts were found to catalyze the hydroboration of aryl and alkyl alkenes with good functional group tolerance.
R. Agahi, A. J. Challinor, N. B. Carter, S. P. Thomas, Org. Lett., 2019, 21, 993-997.

Bench-stable 1,8-diaminonaphthalene-protected diboronic acid (B₂(dan)₂) can be used for Cu-catalyzed borylation of styrene derivatives. The reactions proceeded in good yields in a highly selective manner.
T. Yasuda, Y. Yoshigoe, S. Saito, Org. Lett., 2023, 25, 2093-2097.

Borylation of primary and secondary alkyl chlorides, bromides, and iodides with diboron proceeded in the presence of copper(I)/Xantphos as catalyst and a stoichiometric amount of K(O-t-Bu) as base. Menthyl halides afforded the corresponding borylation product with excellent diastereoselectivity, whereas (R)-2-bromo-5-phenylpentane gave a racemic product.
H. Ito, K. Kubota, Org. Lett., 2012, 14, 890-893.

Aliphatic, aromatic, heteroaromatic, vinyl, or allylic Grignard reagents react with pinacolborane at ambient temperature in tetrahydrofuran to afford the corresponding pinacolboronates. The initially formed dialkoxy alkylborohydride intermediate quickly eliminates hydridomagnesium bromide and affords the product boronic ester in very good yield. This reaction also can be carried out under Barbier conditions.
J. W. Clary, T. J. Rettenmaier, R. Snelling, W. Bryks, J. Banwell, W. T. Wipke, B. Singaram, J. Org. Chem., 2011, 76, 9602-9610.

Hydroboration of terminal and internal aliphatic alkenes with pinacolborane was carried out at room temperature in the presence of dppm and [Ir(cod)Cl]₂ resulting in addition of the boron atom to the terminal carbon with a selectivity of more than 99%. A complex prepared from dppe and [Ir(cod)Cl]₂ resulted in the best yields for vinylarenes.
Y. Yamamoto, R. Fujikawa, T. Umemoto, N. Miyaura, Tetrahedron, 2004, 60, 10695-10700.

A transition-metal-free reaction of alkyl sulfonylhydrazones with alkyl boronic acids provides C(sp³)-rich and sterically hindered alkyl boron reagents in a practical and modular manner. The reaction offers broad generality and functional group tolerance.
Y. Yang, J. Tsien, A. B. David, J. M. E. Hughes, R. R. Merchant, T. Qin, J. Am. Chem. Soc., 2021, 143, 471-480.

An efficient hydroboration of aliphatic 1,1-disubstituted alkenes with pinacolborane using a chiral phosphine-Cu catalyst provides enantiomerically enriched β-chiral alkyl pinacolboronates from a range of 1,1-disubstituted alkenes with high enantioselectivity.
W. J. Jang, S. M. Song, J. H. Moon, J. Y. Lee, J. Yun, J. Am. Chem. Soc., 2017, 139, 13660-13663.

A novel chiral iminopyridine oxazoline (IPO) ligand enables a highly regio- and enantioselective iron-catalyzed anti-Markovnikov hydroboration of 1,1-disubstituted aryl alkenes. This distinct class of reactive IPO ligands will likely be of high value for a large variety of asymmetric transformations using first-row transition metals.
J. Chen, T. Xi, Z. Lu, Org. Lett., 2014, 16, 6452-6455.

A Ni-catalyzed arylboration converts substituted alkenes, aryl bromides, and diboron reagents to products that contain a tertiary or quaternary carbon and a synthetically versatile carbon-boron bond with control of stereoselectivity and regioselectivity. In addition, the method is useful for the synthesis of saturated nitrogen heterocycles.
S. R. Sardini, A. L. Lambright, G. L. Trammel, H. M. Omer, P. Liu, M. K. Brown, J. Am. Chem. Soc., 2019, 141, 9391-9400.

An efficient ligand-free copper-catalyzed borylation offers Markovnikov-selectivity in the reaction of bis(pinacolato)diboron with allyl arenes, while the regioselectivity is completely opposite when styrene derivatives are used as substrates.
Y. Wen, J. Xie, C. Deng, C. Li, J. Org. Chem., 2015, 80, 4142-4147.

A cobalt-catalyzed [4,3]-hydroboration of 1,3-dienes with HBPin provides nearly enantiopure homoallylic boronate esters. A cationic cobalt(I) complex of (R,R)-MeO-BIBOP is a very efficient catalyst while also providing excellent regioselectivities and enantioselectivities for a broad range of substrates.
M. M. Parsutkar, S. Bhunia, M. Majumder, R. F. Lalisse, C. M. Hadad, T.V. RajanBabu, J. Am. Chem. Soc., 2023, 145, 7462-7481.

Cobalt complexes generated from Co(acac)₂ and bisphosphine ligands catalyze asymmetric hydroboration reactions of fluoroalkyl-substituted terminal alkenes with pinacolborane (HBpin) to afford the corresponding chiral alkylboronates containing fluoroalkyl-substituted stereogenic carbon centers with high enantioselectivity.
M. Hu, B. B. Tan, S. Ge, J. Am. Chem. Soc., 2022, 144, 15333-15338.

A nickel-catalyzed 1,2-arylboration of vinylarenes with aryl halides provides various 2-boryl-1,1-diarylalkanes, which constitute a class of significant pharmacophores, in the presence of bis(pinacolato)diboron under mild reaction conditions. This three-component cascade reaction exhibits good functional group tolerance and excellent chemo- and stereoselectivity.
W. Wang, C. Ding, H. Pang, G. Yin, Org. Lett., 2019, 21, 3968-3971.

A mild, efficient, highly regio- and enantioselective copper-catalyzed hydroboration of 1,1-diaryl substituted alkenes with bis(pinacolato)diboron provides a series of valuable β,β-diaryl substituted boronic esters with high enantiomeric purity. Moreover, this approach is also be suitable for hydroboration of α-alkyl styrenes for the synthesis of enantioenriched β,β-arylalkyl substituted boronic esters.
Z. Wang, X. He, R. Zhang, G. Zhang, G. Xu, Q. Zhang, T. Xiong, Q. Zhang, Org. Lett., 2017, 19, 3067-3070.

A very active cobalt catalyst enables a facile anti-Markovnikov hydroboration of sterically hindered terminal alkenes. Notably, these hydroboration reactions proceed in neat substrates at 23°C. With internal olefins, the cobalt catalyst provides a convenient method for hydrofunctionalization of remote C-H bonds by placing the boron substituent exclusively at the terminal positions of an alkyl chain.
J. V. Obligacion, P. J. Chirik, J. Am. Chem. Soc., 2013, 135, 19107-19110.

Highly Selective Bis(imino)pyridine Iron-Catalyzed Alkene Hydroboration
J. V. Obligacion, P. J. Chirik, Org. Lett., 2013, 15, 2680-2683.

Efficient and site selective boron-copper addition processes involving acyclic and cyclic disubstituted aryl olefins are promoted with a readily available N-heterocyclic carbene (NHC) complex. In situ protonation of the C-Cu bond in the presence of MeOH leads to efficient catalyst turnover, constituting a net Cu-catalyzed hydroboration process.
Y. Lee, A. H. Hoveyda, J. Am. Chem. Soc., 2008, 131, 3160-3161.

Cobalt complexes of iminopyridine-oxazoline (IPO) ligands can be applied to the asymmetric hydroboration of 1,1-disubstituted aryl alkenes to afford α-alkyl-β-pinacolatoboranes with exclusive regioselectivity in high yields with up to 99.5% ee. An efficient synthesis of naproxen is described.
L. Zhang, Z. Zuo, X. Wan, Z. Huang, J. Am. Chem. Soc., 2014, 136, 15501-15504.

A simple protocol for the borylation of alkenes with use of impregnated copper on magnetite showed a very broad scope. All type of olefins could be used with similar results. The catalyst can be magnetically removed and reused several times, showing similar activity.
R. Cano, D. J. Ramón, M. Yus, J. Org. Chem., 2010, 75, 3458-3460.

Arylboration of vinylarenes and methyl crotonate with aryl halides and bis(pinacolato)diboron by cooperative Pd/Cu catalysis gives 2-boryl-1,1-diarylethanes and α-aryl-β-boryl ester in a regioselective manner. The reaction is compatible with various functionalities and can be scaled-up to a gram scale.
K. Semba, Y. Nakao, J. Am. Chem. Soc., 2014, 136, 7567-7570.

An enantioselective Cu-catalyzed borylative cross-coupling reaction of alkenes, bis(pinacolato)diboron, and methyl iodide provides the desired methylboration products with excellent diastereoselectivities and enantioselectivities.
B. Chen, P. Cao, Y. Liao, M. Wang, J. Liao, Org. Lett., 2018, 20, 1346-1349.

Reduced cobalt catalysts effect selective 1,2-, 1,4-, or 4,3-additions of pinacolborane to various 1,3-dienes depending on the ligands chosen. Regio- and enantioselective 1,2-hydroborations of 2-substituted 1,3-dienes are best accomplished using a catalyst prepared via activation of a chiral phosphinooxazoline-cobalt(II) complex with zinc and NaBARF.
K. Duvvuri, K. R. Dewese, M. M. Parsutkar, S. M. Jing, M. M. Mehta, J. Galluci, T. V. RajanBabu, J. Am. Chem. Soc., 2019, 141, 7365-7375.

A convenient method for the synthesis of 1,1-diboronates from the corresponding N-tosylhydrazones is also applicable to 1-silyl-1-boron compounds. Derivatization and consecutive Pd-catalyzed cross-coupling reactions with 1,1-boronates were also explored, demonstrating the synthetic potential of 1,1-diboronates.
H. Li, X. Shangguan, Z. Zhang, S. Huang, Y. Zhang, J. Wang, Org. Lett., 2014, 16, 448-451.

(E)- and (Z)-silyl and aryl-subsituted homoallylic methanesulfonates were converted to the corresponding cis- and trans-1-silyl-2-borylcyclobutanes as well as 1-phenyl-2-borylcyclobutanes in the presence of a CuCl/dppp catalyst, bis(pinacolato)diboron, and K(O-t-Bu)in THF. Stereospecific derivatizations of the cis- and trans-borylcyclobutanes were carried out to demonstrate the utility of the borylcyclobutanes.
H. Ito, T. Toyoda, M. Sawamura, J. Am. Chem. Soc., 2010, 132, 5990-5992.

Highly strained bicyclo[1.1.0]butyl boronate complexes, which were prepared by reacting boronic esters with bicyclo[1.1.0]butyl lithium, react with a wide range of electrophiles to form a diverse set of 1,1,3-trisubstituted cyclobutanes with high diastereoselectivity via difunctionalization of the strained central C-C σ-bond of the bicyclo[1.1.0]butyl unit.
S. H. Bennett, A. Fawcett, E. H. Denton, T. Biberger, V. Fasano, N. Winter, V. K. Aggarwal, J. Am. Chem. Soc., 2020, 142, 16766-16775.

The use of N-oxides in butanol as solvent enables a site-selective oxidation of vicinal bis(boronates) with good efficiency and selectivity across a range of substrates to provide 2-hydro-1-boronic esters, which are shown to be versatile intermediates in the synthesis of chiral building blocks.
L. Yan, J. P. Morken, Org. Lett., 2019, 21, 3760-3763.

Bidentate Oxazoline-substituted imidazolium salts based on [2.2]paracyclophane with planar and central chirality can be used as ligand in Cu(I)-catalyzed asymmetric β-boration of α,β-unsaturated esters, giving the desired products in high enantioselectivities and yields.
Z. Niu, J. Chen, Z. Chen, M. Ma, C. Song, Y. Ma, J. Org. Chem., 2015, 80, 602-608.

Cobalt catalysis enables mild reaction conditions for efficient and highly regio- and enantioselective hydroboration of α-alkyl- and α-aryl- acrylates, giving β-borylated propionates. These intermediates could serve as valuable chiral synthons, some from feedstock carbon sources, for the synthesis of propionate-bearing motifs including polyketides and related molecules.
M. D. Patil, K. K. Ghosh, T. V. RajanBabu, J. Am. Chem. Soc., 2024, 146, 6604-6617.

An unprecedented nickel-catalyzed reductive borylation of enaminones provides β-ketone boronic esters via a challenging transformation of an alkenyl C(sp²)-N bond. While B₂pin₂ plays a dual role in this process, water serves as the hydrogen source.
X. Li, Z. Chen, Y. Liu, N. Luo, W. Chen, C. Liu, F. Yu, J. Huang, J. Org. Chem., 2022, 87, 10349-10358.

An enantioselective copper-catalyzed borylacylation of aryl olefins with acyl chlorides and bis-(pinacolato)diboron proceeds with a 2 mol % catalyst loading and is generally completed within 30 min at room temperature. The resulting chiral β-borylated ketones are versatile intermediates in organic synthesis.
Z. Yang, P. Li, H. Lu, G. Li, J. Org. Chem., 2021, 86, 4616-4624.

Cu[(S)-(R)-ppfa]Cl and AgNTf₂ as catalyst enable an asymmetric conjugate addition of B₂pin₂ onto α-functionalized α,β-unsaturated carbonyl compounds under mild, neutral conditions in the presence of an alcohol. AgNTf₂ and alcohols play crucial roles for achieving high catalytic activity and enantio- and diastereoselectivity.
J.-B. Xie, S. Lin, S. Qiao, G. Li, Org. Lett., 2016, 18, 3926-3929.

Using bis(pinacolato)diboron, catalytic amounts of Cu^II, and various amine bases in water under atmospheric conditions at rt, acyclic and cyclic α,β-unsaturated ketones and esters are β-borylated in good yield. Mechanistic investigations suggest that the role of the amine is not only to coordinate to Cu^II but also to activate a nucleophilic water molecule to form a reactive sp²-sp³ diboron complex.
S. B. Thorpe, J. A. Calderone, W. L. Santos, Org. Lett., 2012, 14, 1918-1921.

A simple protocol for the borylation of alkenes with use of impregnated copper on magnetite showed a very broad scope. All type of olefins could be used with similar results. The catalyst can be magnetically removed and reused several times, showing similar activity
R. Cano, D. J. Ramón, M. Yus, J. Org. Chem., 2010, 75, 3458-3460.

A copper(I)-chiral secondary diamine complex catalyzes an enantioselective conjugate boration of β,β-disubstituted enones in high yields and up to 99% ee. The resulting chiral tertiary organoboronates can be converted to enantiomerically enriched β-hydroxy ketones without any racemization.
I-H. Chen, M. Kanai, M. Shibasaki, Org. Lett., 2010, 12, 4098-4101.

A N-heterocyclic carbene (NHC) copper(I) complex generated in situ by the reaction of Cu₂O and a planar and centrally chiral bicyclic 1,2,4-triazolium salt was an efficient catalyst for the asymmetric β-boration of acyclic enones, producing β-boryl ketones in high yields and enantioselectivities.
L. Zhao, Y. Ma, F. He, W. Duan, J. Chen, C. Song, J. Org. Chem., 2013, 78, 1677-1681.

A new planar and central chiral bicyclic triazolium ligand enables a highly efficient copper-catalyzed asymmetric conjugate boration. This protocol gave various chiral secondary alkylboronates in very good ee. A preliminary mechanistic study supports the bifunctional nature of the catalyst.
L. Zaho, Y. Ma, W. Duang, F. He, J. Chen, S. Soung, Org. Lett., 2012, 14, 5780-5783.

Regioselective copper-catalyzed boracarboxylation of vinyl arenes with bis(pinacolato)diboron and carbon dioxide provides boron-functionalized α-aryl carboxylic acids in good yields. The synthetic utility of the transformation was shown through subsequent derivatization of the carbon-boron bond yielding formal hydroxy- and fluorocarboxylation products as well as anionic difluoroboralactones.
T. W. Butcher, E. J. McClain, T. G. Hamilton, T. M. Perrone, K. M. Kroner, G. C. Donohoe, N. G Akhmedov, J. L. Petersen, B. V. Popp, Org. Lett., 2016, 18, 6428-6431.

A catalytic enantioselective conjugate boration of β-substituted cyclic enones in the presence of a QuinoxP*-CuOtBu complex produced enantiomerically enriched tertiary organoboronates. The substrate scope was broad, and high enantioselectivity was produced using both β-aromatic and aliphatic (linear and branched)-substituted cyclic enones with five- to seven-membered ring sizes.
I-H. Chen, L. Yin, W. Itano, M. Kanai, M. Shibasaki, J. Am. Chem. Soc., 2009, 131, 11284-11285.

(η⁶-mes)IrBpin₃ or [Ir(COD)OMe]₂ catalyzes the borylation of cyclopropanes in the presence of the phenanthroline derivative 2,9-Me₂phenanthroline as ligand. The borylation occurs selectively at the methylene C-H bonds of the cyclopropane ring in high diasteroselectivities. The cyclopropylboronate esters can be converted to trifluoroborate salts, boronic acids, cyclopropylarenes, cyclopropylamines, and cyclopropanols.
C. W. Liskey, J. F. Hartwig, J. Am. Chem. Soc., 2013, 135, 3375-3378.

A (NHC)AgCl complex catalyzes an efficient hydroborylation of cyclopropenes with B₂pin₂, delivering a variety of cyclopropylboronates in a stereoselective manner under mild reaction conditions. The cyclopropylboronates can easily be transformed into functionalized cyclopropanes.
M. Huang, C. Zhou, K.-F. Yang, Z. Li, G.-Q. Lai, P. Zhang, J. Org. Chem., 2023, 88, 13838-13846.

Rhodium-catalyzed asymmetric hydroboration of 3,3-disubstituted cyclopropenes gave 2,2-disubstituted cyclopropyl boronates with high degrees of diastereo- and enantioselectivity. Suzuki cross-coupling reaction of selected cyclopropylboronic derivatives produced corresponding optically active aryl- and vinylcyclopropanes in good yields.
M. Rubina, M. Rubin, V. Gevorgyan, J. Am. Chem. Soc., 2003, 125, 7198-7199.

A dramatic rate acceleration in the copper-catalyzed addition of bis(pinacolato)diboron to α,β-unsaturated carbonyl compounds was realized by adding alcohol additives. Various α,β-unsaturated carbonyl compounds were reacted to the corresponding β-boryl carbonyl compounds in high yields.
R. Varala, S. Nuvula, S. R. Adapa, J. Org. Chem., 2006, 71, 8283-8286.

A nickel catalyst system enables the β-boration of di-, tri-, and tetrasubstituted α,β-unsaturated esters and amides with bis(pinacolato)diboron in good yields.
K. Hirano, H. Yorimitsu, K. Oshima, Org. Lett., 2007, 9, 5031-5033.

Aryl cyclopropyl ketones undergo nickel-catalyzed borylative ring opening with bis(pinacolato)diboron to yield 4-oxoalkylboronates in good yield.
Y. Sumida, H. Yorimitsu, K. Oshima, J. Org. Chem., 2009, 74, 3196-3198.

In a catalytic enantioselective nucleophilic borylation, a series of aldehydes reacted with B₂pin₂ in the presence of a copper(I)/DTBM-SEGPHOS complex as catalyst and MeOH as a proton source to give the corresponding optically active α-alkoxyorganoboronate esters with excellent enantioselectivities. These products can readily be converted to chiral alcohol derivatives through stereospecific C-C bond forming reactions.
K. Kubota, E. Yamamoto, H. Ito, J. Am. Chem. Soc., 2015, 137, 420-424.

A highly efficient deoxygenative haloboration of aldehydes provides secondary α-haloboronates. Even tertiary α-haloboronates can be readily prepared via the same strategy with ketones. Furthermore, enantioselective chloroboration of carbonyls was successfully achieved to give chiral secondary or tertiary α-chloroboronates.
D. Wang, J. Zhou, Z. Hu, T. Xu, J. Am. Chem. Soc., 2022, 144, 22870-22876.

Visible-light-induced B-H insertions of HBpin with acylsilane proceed in an atom-economical, metal-free, and operationally simple way with broad substrate scope under mild reaction conditions, to provide important α-alkoxyorganoboronate esters in quantitative yields.
J.-H. Ye, L. Quach, T. Paulisch, F. Glorius, J. Am. Chem. Soc., 2019, 141, 16227-16231.

Diboration of ketones with (ICy)CuOt-Bu as catalyst provides access to various tertiary α-hydroxyboronate esters. The catalyst was generated in situ with (ICy)CuCl and NaOt-Bu to afford a more efficient catalyst than the preformed (ICy)CuOt-Bu. Treatment of the resulting products with silica gel affords the corresponding α-hydroxyboronate esters.
M. L. McIntosh, C. M. Moore, T. B. Clark, Org. Lett., 2010, 12, 1996-1999.

A Cu-catalyzed regioselective and stereospecific aminoboration of styrenes with bis(pinacolato)diboron and O-benzoyl-N,N-dialkylhydroxylamines delivers β-aminoalkylboranes in good yields. The Cu catalysis enables introduction of both amine and boron moieties to C-C double bonds simultaneously in a syn fashion. Moreover, the use of a chiral biphosphine ligand, (S,S)-Me-Duphos, provides optically active β-aminoalkylboranes.
N. Matsuda, K. Hirano, T. Satoh, M. Miura, J. Am. Chem. Soc., 2013, 135, 4934-4937.

Hydroboration of α,β-unsaturated carbonyl substrates followed by 1,2-elimination provides gem-difluoroalkenes under mild conditions. gem-Difluoroalkenes can be converted into β-CF₂H- and β-CFH₂-α,β-unsaturated carbonyls.
S. An, J. Zhang, G. Jiang, Synlett, 2021, 32, 91-94.

A catalytic enantioselective diboration of vinyl boronate esters furnishes chiral tris(boronates). Subsequent intermolecular or intramolecular deborylative alkylation occurs in a diastereoselective fashion.
J. R. Coombs, L. Zhang, J. P. Morken, J. Am. Chem. Soc., 2014, 136, 16140-16143.

A Co(I)-catalyzed, selective preparation of 1,1,1-tris(boronates) from vinylarenes and bis(pinacolato)diboron occurs at ambient temperature with excellent selectivity, high yields, and good functional group tolerance via double dehydrogenative borylations to generate an 1,1-diborylalkene intermediate followed by a hydroboration with pinacolborane formed in situ to yield the desired 1,1,1-tris(boronate).
L. Zhang, Z. Huang, J. Am. Chem. Soc., 2015, 137, 15600-15603.

An Ir-catalyzed enantioselective C(sp3)-H borylation of cyclopropanecarboxamides using a chiral bidentate boryl ligand provides β-borylated products with good to excellent enantioselectivities. The borylated products can be used as versatile precursors.
Y. Shi, Q. Gao, S. Xu, J. Am. Chem. Soc., 2019, 141, 10599-10604.

Related

The reaction of 1,1-bis(pinacolboronate) esters with alkyl halides promoted by metal alkoxides provides organoboronate compounds via alkoxide-induced deborylation and generation of a boron-stabilized carbanion.
K. Hong, X. Liu, J. P. Morken, J. Am. Chem. Soc., 2014, 136, 10581-10584.

A nickel-catalyzed Negishi cross-coupling of alkyl halides, including unactivated tertiary halides, with the boron-stabilized organozinc reagent BpinCH₂ZnI provides versatile organoboron products with high functional-group tolerance.
P. Guo, H. Jin, J. Han, L. Xu, P. Li, M. Zhan, Org. Lett., 2023, 25, 1246-1251.

A copper-catalyzed regio- and enantioselective hydroallylation of alkenyl boronates and boramides with allylic phosphates in the presence of hydrosilanes enables an efficient synthesis of a broad range of homoallylic alkylboron compounds in good yields and with high enantioselectivities.
J. T. Han, W. J. Jang, N. Kim, J. Yun, J. Am. Chem. Soc., 2016, 138, 15146-15149.

A Ni-catalyzed reductive allylation of α-chloroboronates with allyl sulfones efficiently provides the corresponding homoallylic boronates, which could be readily converted into valuable homoallylic alcohols or amines or 1,4-diboronates. This reaction features a broad substrate scope with good functional group compatibility.
Y. Lou, J. Qiu, K. Yang, F. Zhang, C. Wang, Q. Song, Org. Lett., 2021, 23, 4564-4569.

In the presence of IMes-Cu catalyst, a tandem hydrocupration/allylation of alkenyl boronates with allyl phosphate efficiently proceeds in the presence of a hydrosilane via in situ generated Β-α-copper intermediates. Mono- and disubstituted alkenyl boronates were effective in the reaction with terminal allyl phosphates, but trisubstituted substrates showed limited reactivity.
W. J. Jang, J. T. Han, J. Yun, Synthesis, 2017, 49, 4753-4758.

In a Cu/(NHC)-catalyzed S_N2'-selective substitution reaction of allylic electrophiles with gem-diborylalkanes, differently substituted gem-diborylalkanes and allylic electrophiles can be employed, and various synthetic valuable functional groups are tolerated. The use of chiral N-heterocyclic carbene (NHC) ligands enables an asymmetric version.
Z.-Q. Zhang, B. Zhang, X. Lu, J.-H. Liu, X.-Y. Lu, B. Xiao, Y. Fu, Org. Lett., 2016, 18, 952-955.

An iridium-catalyzed enantioconvergent coupling of the versatile boron-stabilized organozinc reagent BpinCH₂ZnI with racemic branched allylic carbonates provides various chiral homoallylic organoboronic esters in good yields with excellent enantioselectivities. The homoallylboronates can easily be converted to other useful families of compounds.
P. Guo, M. Zhan, J. Org. Chem., 2021, 86, 9905-9913.

The Suzuki-Miyaura cross-coupling reaction between a diborylmethane derivative and allyl halides or benzyl halides proceeded efficiently in the presence of an appropriate Pd-catalyst at room temperature. The present approach provides functionalized homoallylboronates and alkylboronates with excellent regio- and chemoselectivities.
K. Endo, T. Ohkubo, T. Ishioka, T. Shibata, J. Org. Chem., 2012, 77, 4826-4831.

The combination of copper(I) bromide and H₈-BINOL derived phosphoramidite ligand catalyzes an enatiotopic-group-selective allylation of gem-diborylalkanes with allyl bromides to provide enantioenriched homoallylic boronate esters in good yields with high enantiomeric ratios under mild conditions.
M. Kim, B. Park, M. Shin, S. Kim, J. Kim, M.-H. Baik, S. H. Cho, J. Am. Chem. Soc., 2021, 143, 1069-1077.

A general method for accessing sterically encumbered geminal bis(boronates) is based on a formal umpolung strategy. Readily available 1,1-diborylalkanes were first converted into the corresponding α-halogenated derivatives, which then serve as electrophilic components, undergoing a formal substitution with a diverse array of nucleophiles to form a series of C−C, C−O, C−S, and C−N bonds.
P.-F. Ning, Y. Wei, X.-Y. Chen, Y.-F. Yang, F.-C. Gao, K. Hong, Angew. Chem. Int. Ed., 2023, 62, e202315232.

A transition metal-free deborylative cyclization of geminal bis(boronates) bearing a leaving group provides cyclopropylboronates with high diastereoselectivity. When derivatives of optically active epoxides were used as the starting materials, enantioenriched cyclopropylboronates could be efficiently prepared.
X.-Y. Chen, F.-C. Gao, P.-F. Ning, Y. Wei, K. Hong, Angew. Chem. Int. Ed., 2023, 62, e202302638.

1,2-Bis-boronic esters are versatile intermediates that enable the rapid elaboration of simple alkene precursors. A photoredox-catalyzed mono-deboronation generates primary β-boryl radicals that undergo rapid 1,2-boron shift to form thermodynamically favored secondary radicals, allowing for selective transformation of the more hindered boronic ester.
D. Kaiser, A. Noble, V. Fasano, V. K. Aggarwal, J. Am. Chem. Soc., 2019, 141, 14104-14109.