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Synthesis of vinylboronic acids and vinylboronates


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Miyaura Borylation Reaction

Recent Literature

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.

Tropylium salts promote the hydroboration reaction of alkynes to provide a broad range of vinylboronates. Similar metal-free hydroboration reactions of alkenes and epoxides can also be efficiently catalyzed by the same tropylium catalysts. Experimental studies and DFT calculations suggested that the reaction is triggered by the hydride abstraction of pinacolborane with tropylium ion.
N. N. H. Ton, B. K. Mai, T. V. Nguyen, J. Org. Chem., 2021, 86, 9117-9133.

Carboxylic acids are able to catalyze the direct hydroboration of various terminal and internal alkynes with pinacolborane without using any metal catalysts. This hydroboration exhibits a broad functional groups compatibility and gives the corresponding alkenyl diboronates and monoboronates in very good yields with exclusive regio- and stereoselectivities.
H. E. Ho, M. Asao, Y. Yamamoto, T. Jin, Org. Lett., 2014, 16, 4670-4673.

An iron complex bearing a pyrrolide-based PNP pincer ligand enables a catalyzed hydroboration of alkynes with pinacolborane, where the corresponding E-isomers are obtained selectively.
K. Nakajima, T. Kato, Y. Nishibayashi, Org. Lett., 2017, 19, 4323-4326.

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.

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.

A conjugated bis-guanidinate (CBG)-supported aluminum dihydride complex catalyzes a chemoselective hydroboration of various nitriles and alkynes. The reaction leaves other reducible groups intact. Moreover, aluminum-catalyzed hydroboration is expanded to more challenging substrates such as alkene, pyridine, imine, carbodiimide, and isocyanides.
N. Sarkar, S. Bera, S. Nembenna, J. Org. Chem., 2020, 85, 4999-5009.

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.

Methylpentanediolborane can be prepared easily by reaction of hexyleneglycol with borane dimethylsulfide or B2H6 generated from NaBH4 and I2. MPBH hydroborates stereo- and regioselectively highly functionalized alkynes. MPBH compares favorably with pinacolborane in terms of reactivity. The obtained vinylboronic esters are air- and chromatography-stable.
N. PraveenGanesh, S. d'Hondt, P. Y. Chavant, J. Org. Chem., 2007, 72, 4510-4514.

Preparation of (E)-1-Alkenylboronic Acid Pinacol Esters via Transfer of Alkenyl Group from Boron to Boron
K. Shirakawa, A. Arase, M. Hoshi, Synthesis, 2004, 1814-1820.

A ruthenium hydride pincer complex catalyzes the anti-Markovnikov addition of pinacolborane to terminal alkynes yielding Z-vinylboronates at mild conditions. The catalytic cycle involves rearrangement of coordinated alkyne to Z-vinylidene as a key step for the apparent trans-hydroboration.
C. Gunanathan, M. Hölscher, F. Pan, W. Leitner, J. Am. Chem. Soc., 2012, 134, 14349-14352.

Ferric chloride catalyzes an efficient monoborylation of alkynes using bis(pinacolato)diboron to provide E-vinyl boronates with high regio- and stereoselectivity in good to excellent yields. Using iron nanoparticles, a high catalytic activity was observed and the catalyst could be recovered simply by using an external magnetic field. The magnetic nanoparticles were recycled six times without any significant loss of catalytic activity.
V. S. Rawat, B. Sreedhar, Synlett, 2014, 25, 1132-1136.

A silver(I)-N-heterocyclic carbene complex is a potent catalyst for formal hydroboration of alkynes, providing a variety of borylalkenes with high regio- and stereoselectivity. Under silver catalysis, allenes also undergo regioselective hydroboration to give borylalkenes.
H. Yoshida, I. Kageyuki, K. Takaki, Org. Lett., 2014, 16, 3512-3515.

1-Alkenylboronic acid pinacol esters can be synthesized via a palladium-catalyzed cross-coupling reaction of 1-alkenyl halides or triflates with bis(pinacolato)diboron in toluene at 50°C in the presence of potassium phenoxide and PdCl2(PPh3)2·2PPh3.
K. Takahashi, J. Takagi, T. Ishiyama, N. Miyaura, Chem. Lett., 2000, 126-127.

A high α-selectivity of a ligand controlled selective hydroborylation of terminal alkynes to α-vinylboronates using a Pd catalyst can be switched to furnish β-vinylboronates by altering the ligand from a trialkylphosphine to N-heterocyclic carbene. Various terminal alkynes furnish the corresponding α- or β-vinylboronates in excellent selectivity and yield.
D. P. Ojha, K. R. Prabhu, Org. Lett., 2016, 18, 432-435.

A Zr-catalyzed carboalumination of terminal alkynes followed by in situ transmetalation with i-PrOBpin enabels an operationally simple and scalable synthesis of trisubstituted alkenyl boronic esters in good yields, with excellent regioselectivity and perfect stereoselectivity.
O. Zhurakovskyi, R. M. P. Dias, A. Noble, V. K. Aggarwal, Org. Lett., 2018, 20, 3136-3139.

Reliable, operationally simple, catalytic α-selective hydroalumination reactions proceed in the presence of diisobutylaluminum hydride and (Ni(dppp)Cl2), and, unlike uncatalyzed transformations, generate little or no alkynylaluminum byproducts. The derived α-vinyl halides and boronates can be synthesized through direct treatment with the appropriate electrophiles.
F. Gao, A. H. Hoveyda, J. Am. Chem. Soc., 2010, 132, 10961-10963.

A Pd-catalyzed direct borylation of various 1,1- and 1,2-disubstituted alkenes provides trisubstituted alkenyl boronic esters with outstanding yields and excellent E/Z selectivities via a boryl-Heck pathway. Several derivatizations of the alkenyl boronic esters allow access to diverse, stereodefined, functionalized olefins.
W. B. Reid, D. A. Watson, Org. Lett., 2018, 20, 6822-6826.

A Cu/TEMPO catalyst system exhibits both excellent reactivity and selectivity for the synthesis of alkenylboronates from inexpensive alkenes and pinacol diboron. This approach enables a direct functionalization of both aromatic and aliphatic terminal alkenes.
W. Lu, Z. Shen, Org. Lett., 2019, 21, 142-146.

A Pd-catalyzed direct borylation of various 1,1- and 1,2-disubstituted alkenes provides trisubstituted alkenyl boronic esters with outstanding yields and excellent E/Z selectivities via a boryl-Heck pathway. Several derivatizations of the alkenyl boronic esters allow access to diverse, stereodefined, functionalized olefins.
W. B. Reid, D. A. Watson, Org. Lett., 2018, 20, 6822-6826.

A boryl-Heck reaction of terminal alkenes with commercially available catecholchloroborane (catBCl) as an electrophilic boron reagent provides trans-alkenyl boronic esters. In situ transesterification allows for rapid access to various boronic esters, amides, and other alkenyl boron adducts.
W. B. Reid, J. J. Spillane, S. B. Krause, D. A. Watson, J. Am. Chem. Soc., 2016, 138, 5539-5542.

Ni(II) catalyzes a borylation of conjugated alkenyl methyl ethers with B2pin2. Both E/Z isomers of alkenyl ethers are converted into (E)-alkenyl boronic esters. This chemoselective method tolerates aryl ether, ester, amide, and thioether groups.
X. Qiu, Y. Li, L. Zhou, P. Chen, F. Li, Y. Zhang, Y. Ling, Org. Lett., 2020, 22, 6424-6428.

A palladium-catalyzed oxidative borylation reaction of readily available N-tosylhydrazones provides di-, tri-, and tetrasubstituted alkenylboronates. This highly efficient and practical reaction offers mild conditions, broad substrate scope, and good functional group tolerance. One-pot Suzuki coupling and other transformations highlight the synthetic utility of the approach.
Y. Ping, R. Wang, Q. Wang, T. Chang, J. Huo, M. Lei, J. Wang, J. Am. Chem. Soc., 2021, 143, 9769-9780.

An efficient Cu-catalazed borylation of propargylic alcohols provides vinyl-, allyl-, and (E)-2-boryl allylboronates in very good yield with a broad substrate scope under mild conditions. Isolation of an allenyl boronate as the reaction intermediate suggests that an insertion-elimination-type reaction, followed by borylcupration, is involved.
L. Mao, R. Bertermann, K. Emmert, K. J. Szabo, T. B. Marder, Org. Lett., 2017, 19, 6586-6589.

In a copper-catalyzed formal carboboration of alkynes, a C-B bond and a C-C bond are created in a single catalytic cycle. The reaction proceeds with high regioselectivity and syn-stereoselectivity to form tri- and tetrasubstituted vinylboronic esters from commercially available bis(pinacolato)diboron. A subsequent cross-coupling reaction gives access to highly substituted alkenes.
R. Alfaro, A. Parra, J. Alemán, J. L. G. Ruano, M. Tortosa, J. Am. Chem. Soc., 2012, 134, 15165-15168.

In a copper-catalyzed regio- and stereoselective borylalkylation of dialkylsubstituted internal alkynes with bis(pinacolato)diboron and alkyl halides, a borylcopper species containing a novel π-accepting N-heterocyclic carbene ligand chemoselectively reacted with unactivated internal alkynes over alkyl halides. The intermediate alkenylcopper species subsequently reacted with alkyl halides, affording the desired products.
T. Itoh, Y. Shimizu, M. Kanai, J. Am. Chem. Soc., 2016, 138, 7528-7531.

Protoborations of terminal allenes catalyzed by NHC-Cu complexes afford valuable 1,1- or trisubstituted vinylboronates with high site selectivity and stereoselectivity. The scope of the method, application to natural product synthesis, and mechanistic details for the observed selectivity are presented.
F. Meng, B. Jung, F. Haeffner, A. H. Hoveyda, Org. Lett., 2013, 15, 1414-1417.

The catalytic property of nanoporous gold for activation of bis(pinacolato)diboron allows an efficient direct diboration of alkynes in a heterogeneous process. The nanoporous gold catalyst is able to cleave the B–B bond of bis(pinacolato)diboron without using any additives.
Q. Chen, J. Zhao, Y. Ishikawa, N. Asao, Y. Yamamoto, T. Jin, Org. Lett., 2013, 15, 5766-5769.

A cobalt-catalyzed method for the diboration of terminal alkynes with B2Pin2 proceeds efficiently at 23°C with excellent 1,1-selectivity and broad functional group tolerance. With the unsymmetrical diboron reagent PinB-BDan, stereoselective 1,1-diboration provided products with two boron substituents that exhibit differential reactivity.
S. Krautwald, M. J. Bezdek, P. J. Chirik, J. Am. Chem. Soc., 2017, 139, 3868-3875.

Rhodium-catalyzed deoxygenations and borylations of ketones with B2pin2 provide alkenes, vinylboronates, and vinyldiboronates. These reactions offer mild reaction conditions, a broad substrate scope, and excellent functional-group compatibility. Mechanistic studies support that the ketones initially undergo a Rh-catalyzed deoxygenation to give alkenes via boron enolate intermediates.
L. Tao, X. Guo, J. Li, R. Li, Z. Lin, W. Zhao, J. Am. Chem. Soc., 2020, 142, 18118-18127.

A gem-diborylation of 2-arylvinyl sulfides with bis(pinacolato)diboron proceeded efficiently with a rhodium catalyst to provide a wide range of (2,2-diborylvinyl)arenes. Mechanistic studies indicate that the reaction proceeds from either of the stereoisomers in a stepwise manner via borylative C-S bond cleavage and subsequent dehydrogenative borylation.
Y. Uetake, M. Isoda, T. Niwa, T. Hosoya, Org. Lett., 2019, 21, 4933-4938.

In a synthesis of 1,1-diboryl alkenes from terminal alkenes, 1,1-regioselective addition is observed for both conjugated and unconjugated alkenes. The method provides a wide range of 1,1-diboryl alkenes.
O. O. Idowu, J. C. Hayes, W. B. Reid, D. A. Watson, Org. Lett., 2021, 23, 4838-4842.

Phosphine-free Pd complexes together with alkenyl or aryl iodides were very efficient catalysts for 1,2-diboration of allenes. This reaction is completely regioselective and highly stereoselective. Monosubstituted allenes afford diboration products with mainly Z stereochemistry.
F.-Y. Yang, C.-H. Cheng, J. Am. Chem. Soc., 2001, 123, 761-762.

Substituted alkynoates undergo borylation in a regio-, stereo-, and chemoselective fashion to afford (Z)-β-boryl-α,β-unsaturated esters in the presence of bis(pinacolato)diboron and catalytic amounts of both copper(II) and 4-picoline. The reaction is performed under mild conditions using water as solvent and open to the atmosphere.
C. L. Peck, J. A. Calderone, W. L. Santos, Synthesis, 2015, 47, 2242-2248.

A tandem sequence in which Cu/Xantphos catalyzes a B2pin2-syn-hydroboration of an alkyne whereas Cu/BINAP serves as a photocatalyst for visible light-mediated isomerization of the resulting alkenyl boronic ester enables a formal anti-hydroboration of activated internal alkynes.
J. Corpas, M. Gomez-Mendoza, J. Ramírez-Cárdenas, V. A. de la Peña O’Shea, P. Mauleón, R. G. Arrayás, J. C. Carretero, J. Am. Chem. Soc., 2022, 144, 13006-13017.

Trialkylphosphines catalyze a regioselective anti-hydroboration of internal alkynes with pinacolborane reagents to provide (E)-disubstituted alkenylboronate compounds. The alkenylboronates can be used for derivatizations, such as protodeborylations, Suzuki-Miyaura couplings, conjugate reductions, and Diels-Alder reactions.
K. Nagao, A. Yamazaki, H. Ohmiya, M. Sawamura, Org. Lett., 2018, 20, 1861-1865.

A base-mediated trans-hydroboration of a wide range of propiolamides provides access to previously elusive primary and secondary (E)-β-borylacrylamides. The use of n-butyllithium and pinacolborane provides the corresponding vinylboronates in very good yields with complete regioselectivity and stereoselectivity.
R. J. Grams, R. G. Fritzemeier, C. Slebodnick, W. L. Santos, Org. Lett., 2019, 21, 6795-6799.

Addition of an allyl copper species to an isocyanate provides access to α-vinyl β-boryl amides in high yields and enantioselectivities. The diversification of these products affords highly useful scaffolds.
S. Byun, A. O. Farah, H. R. Wise, A. Katchmar, P. H.-Y. Cheong, K. A. Scheidt, J. Am. Chem. Soc., 2022, 144, 22850-22857.

4-Substituted 1,2-oxaborol-2(5H)-ols were prepared through copper-catalyzed carbomagnesation of propargyl alcohol, followed by the transmetallation of magnesium to boron in a one-pot procedure. The Suzuki-Miyaura cross-coupling of these new 2,2-disubstituted alkenylboronic acids with aryl halides afforded stereodefined 2,3-disubstituted allyl alcohols in good to excellent yields.
G.-H. Fang, Z.-J. Yan, M.-Z. Deng, Synthesis, 2006, 1148-1154.

A new method for the synthesis of organoborates starting from α,β-unsaturated acetals was developed. The available alkoxy-functionalized butadienyl- and styrylboronic esters cross couple effectively with a broad spectrum of aryl halides under mild conditions. This method provides an effective approach to aromatic ketones.
P. B. Tivola, A. Deagostino, C. Prandi, P. Venturello, Org. Lett., 2002, 4, 1275-1277.

The Cross-coupling reaction of bis(pinacolato)diboron with β-(trifluoromethanesulfonyloxy)-α,β-unsaturated carbonyl compounds was carried out in the presence of PdCl2(PPh3)2-2PPh3 (3 mol%) and KOPh in toluene or K2CO3 in dioxane for the synthesis of cyclic and acyclic β-boryl-α,β-unsaturated esters, amides, and ketones in high yields.
J. Takagi, A. Kamon, T. Ishiyama, N. Miyaura, Synlett., 2002, 1880-1882.

Monobenzofused 1,4-azaborine phosphine ligands uniquely support Pd-catalyzed trans-selective hydroboration of terminal and internal 1,3-enynes to furnish the corresponding dienylboronates in high efficiency and diastereoselectivity.
S. Xu, Y. Zhang, B. Li, S.-Y. Liu, J. Am. Chem. Soc., 2016, 138, 14566-14569.

Alkynylboration of alkynes with alkynyl(pinacol)boranes in the presence of nickel catalysts gave cis-1-borylbut-1-en-3-yne derivatives. Some boryl-substituted enynes were reacted with sp2 halides under Suzuki-Miyaura coupling conditions.
M. Suginome, M. Shirakura, A. Yamamoto, J. Am. Chem. Soc., 2006, 128, 14438-14439.

In the presence of a chiral phosphoramidite ligand, the palladium-catalyzed diboration of allenes can be executed with high enantioselectivity with a range of aromatic and aliphatic allenes. A mechanism is proposed based on isotopic-labeling experiments, stereodifferentiating reactions, kinetic analysis, and computational experiments.
H. E. Burks, S. Liu, J. P. Morken, J. Am. Chem. Soc., 2007, 129, 8766-8773.

Pd-catalyzed diboration of prochiral allenes occurs exclusively at the internal position and is accelerated in the presence of Lewis basic ligands. A chiral ligand was employed, and the enantiomeric excess of a variety of diboration products was found to be in the range of 86-92% ee.
N. F. Pelz, A. R. Woodward, H. E. Burks, J. D. Sieber, J. P. Morken, J. Am. Chem. Soc., 2004, 126, 16328-16329.

An efficient Cu-catalazed borylation of propargylic alcohols provides vinyl-, allyl-, and (E)-2-boryl allylboronates in very good yield with a broad substrate scope under mild conditions. Isolation of an allenyl boronate as the reaction intermediate suggests that an insertion-elimination-type reaction, followed by borylcupration, is involved.
L. Mao, R. Bertermann, K. Emmert, K. J. Szabo, T. B. Marder, Org. Lett., 2017, 19, 6586-6589.

Bromoboration of propyne with BBr3 proceeds in syn-selectivity to produce (Z)-2-bromo-1-propenyldibromoborane, which is prone to stereoisomerization. Treatment with pinacol yields the stable and storable pinacolboronate. Negishi coupling gives trisubstituted (Z)-alkenylpinacolboronates in good yields. Iodinolysis of the boronates affords alkenyl iodides in good yields.
C. Wang, T. Tobrman, Z. Xu, E.-i. Negishi, Org. Lett., 2009, 11, 4092-4095.

A cascade borylation/B-O elimination of propynols and B2pin2 enables an efficient synthesis of tetrasubstituted alkenylboronates in good yields. Further transformations leading to β-diketones and tetrasubstituted alkenes demonstrate the synthetic potential of the alkenylboronates as versatile intermediates in organic synthesis.
Z. Kuang, H. Chen, J. Yan, K. Yang, Y. Lan, Q. Song, Org. Lett., 2018, 20, 5153-5157.

Commercially available chiral ligands enable a widely applicable, practical, and scalable strategy for efficient and enantioselective synthesis of β,γ-unsaturated ketones that contain an α-stereogenic center.
J. del Pozo, S. Zhang, F. Romiti, S. Xu, R. P. Conger, A. H. Hoveyda, J. Am. Chem. Soc., 2020, 142, 18200-18212.

A Cu/Pd-catalyzed borylallenylation of alkynes with propargylic carbonates and bis(pinacolato)diboron enables the synthesis of boryl-substituted ene-allenes. Densely (tetra-, penta-, and hexa-) substituted ene-allenes were synthesized in acceptable yield with high regio- and stereoselectivity. More important molecule structures can be obtained by subsequent modifications.
S.-H. Yu, T.-J. Gong, Y. Fu, Org. Lett., 2020, 22, 2941-2945.


A stereoselective synthesis of tetrasubstituted alkenylboronates, which are useful synthetic intermediates for further functionalizations, was established via the lithiation/nucleophilic addition reaction of 1,1-organodiboronates to carbonyl compounds.
K. Endo, M. Hirokami, T. Shibata, J. Org. Chem., 2010, 75, 3469-3472.

A highly stereoselective boron-Wittig reaction between stable and readily accessible 1,1-bis(pinacolboronates) and aldehydes furnishes various synthetically useful di- and trisubstituted vinyl boronate esters.
J. R. Coombs, L. Zhang, J. P. Morken, Org. Lett., 2015, 17, 1708-1711.

A highly stereoselective boron-Wittig reaction between stable and readily accessible 1,1-bis(pinacolboronates) and aldehydes furnishes various synthetically useful di- and trisubstituted vinyl boronate esters.
J. R. Coombs, L. Zhang, J. P. Morken, Org. Lett., 2015, 17, 1708-1711.

Efficient alkene isomerizations of readily available 1,1-disubstituted alkenylboronate esters provide synthetically valuable trisubstituted alkenylboronates. Either stereoisomer of the target alkenylboronate motif can be obtained by employing different isomerization catalysts.
L. Segura, I. Massad, M. Ogasawara, I. Marek, Org. Lett., 2021, 23, 9194-9198.

A number of alkynyl pinacolboronates were stereoselectively reduced to the cis-alkenyl pinacolboronates via hydroboration with dicyclohexylborane followed by chemoselective protodeboronation using acetic acid. Treatment with potassium hydrogen fluoride smoothly converted these to the corresponding potassium organotrifluoroborates.
G. A. Molander, N. M. Ellis, J. Org. Chem., 2008, 73, 6841-6844.

The cobalt-catalyzed Diels-Alder reaction of alkynyl pinacol boronic esters with various dienes generates cycloadducts in very good regioselectivity. A reaction sequence (Diels-Alder reaction, Suzuki coupling, DDQ oxidation) was successfully performed as a one pot operation without isolation of the intermediates.
G. Hilt, K. I. Smolko, Angew. Chem. Int. Ed., 2003, 42, 2795-2797.

A Fe-catalyzed addition of alkyl radicals, formed from the corresponding alkyl halides, to ethynyl ethynylboronic acid pinacol ester provides Z-vinyl boronates in high stereoselectivity. The method works best for tertiary and secondary alkyl iodides.
G. Barzanò, A. Cheseaux, X. Hu, Org. Lett., 2019, 21, 490-493.

In situ generation of allylic boronates by iridium-catalyzed borylation of cyclic alkenes in the presence of additives, such as methylimidazole and DBU, followed a reaction with aldehydes allows the synthesis of stereodefined homoallylic alcohols. Cycloalkenes without additives as well as acyclic substrates gave vinylic boronates, which were coupled with organohalides in a Suzuki-Miyaura sequence.
V. J. Olsson, K. J. Szabó, J. Org. Chem., 2009, 74, 7715-7723.

1-Alkenylboronic acid pinacol esters have been synthesized via a palladium-catalyzed cross-coupling reaction of bis(pinacolato)diboron with 1-alkenyl halides or triflates in toluene at 50°C in the presence of KOPh in high yields with complete retention of configuration of the double bonds. A one-pot synthesis of unsymmetrical 1,3-dienes via the borylation-coupling sequence has been developed.
J. Takagi, K. Takahashi, T. Ishiyama, N. Miyaura, J. Am. Chem. Soc., 2002, 124, 8001-8006.

The presence of supported gold nanoparticles enables gold-catalyzed silaboration of terminal alkynes with PhMe2SiBpin. The reaction proceeds at ambient conditions in very good yields with a regioselectivity opposite to that observed in the presence of Pd or Pt catalysts. The abnormal regioselectivity is attributed to steric factors imposed by the Au nanoparticle during the 1,2-addition of silylborane to the alkyne.
C. Gryparis, M. Stratakis, Org. Lett., 2014, 16, 1430-1433.

Pd-catalyzed enantioselective diborations of prochiral allenes followed by allylation reactions with primary imines provide vinyl boronates which may be oxidized to give nonracemic Mannich products. Alternatively, enantiomerically enriched homoallylic amine derivatives may be obtained by protonation and Suzuki cross-coupling of the vinyl boronate.
J. D. Sieber, J. P. Morken, J. Am. Chem. Soc., 2006, 128, 74-75.