Table 1 A general overview of the pertinent reports on carbon (sp³)-carbon (sp²) cross-couplings included in this study

Aryl iodides

Ttrialkylboranes and B-alkyl-9-BBN

PdCl2(dppf), NaOH, THF, reflux,

3A

[80]

Aryl iodides and bromides

Alkylboranes

PdCl2(dppf), NaOH, THF, 65 ^◦C

3B

[81,82,83]

Aryl halides

B-boronic acids and a B-alkyl-9-BBN

Pd(OAc)2, SPhos, K3PO4.H2O, THF/Toluene

3C

[84]

Chloroenzynes

B-benzyl-9-BBN

Pd(PPh3)4, Cs2CO3, water

4

[85]

CAr-O electrophiles

B-alkyl-9-BBN

Ni(COD)2, IPr.HCl, CssCO3,

iPr₂ O, 110 °C , 12 h

5A

[89]

Aromatic and alkenyl ethers

B-alkyl-9-BBN

Ni(COD)2, PCy3, base, iPr2O, 110 °C ,

5B, C

[90]

Aryl halides

9-BBN and 1,3-dienes

Pd(dppf)Cl2 or Pd(dppb)Cl2N

6

[91]

β-triflyl enones

B-alkyl-9-BBN

Pd(dppf)Cl2, Cs2CO3,

DMF:THF:H2O, 60 °C , 16 h

7A

[92]

Halogenated pyridine

9-BBN derivatives of L-aspartic acid

Pd(PPh3)4, K3PO4 (aq.), THF

50 °C ,

7B

[93]

Aromatic esters

Alkyl organoboron reagents

Ni(COD)2, dcype, CsF, toluene

8A

[95]

Aroyl fluorides

Alkyl organoboron reagents

Ni(COD)2, dppe, CsF,

8B

[96]

Aryl halides/triflates and vinyl triflates

Potassium alkyltrifluoroborates

PdCl2(dppf)CH2Cl

Cs2CO3, THF: H2O, reflux, 6–72 h

10B

[48, 98]

Aryl and heteroaryl chlorides and bromides

Tertiary trifluoroborate salts

CatacXium-A-Pd G3, Cs2CO3,

tol/water, 90 °C , 18 h

10C

[104]

Aryl bromides

Secondary alkyl β-trifluoroboratoketones and esters

Ir[dFCF3ppy]2(bpy)PF6,

NiCl2 dme, dtbbpy, Cs2CO3,

2,6-lutidine, 1,4-dioxane, hv

11A

[10]

Aryl bromides

α-alkoxyalkyl- and α-acyloxyalkyltrifluoroborates

Ir[dFCF3ppy]2(bpy)PF6,

Ni(COD)2, dtbbpy, K2HPO4, dioxane, hv

11B

[106]

Aryl bromides

Tertiary organotrifluoroborates

reagents

Ir[dFCF3ppy]2(bpy)PF6, Ni(TMHD)₂ or Ni(dtbbpy)(H2O)4Cl2, K2HPO4 or Na2CO3, no additive or ZnBr₂,

dioxane/DMA or DMA, hv, 12–72 h

11C

[107]

Aryl bromides

Trialkylboranes

PdCl₂(dppf), THF, reflux, 2–6 h

13B

[111, 112]

Aryl halides and triflates

NHC–borane complexes

[Pd], Ligand, tol-H₂O or THF-H₂O,

heat or microwave

13C

[113]

Alkenyl and aryl halides

Trialkyl- and triaryl-boranes (generated in situ)

Pd(OAc)2, n-BuAd2P or RuPhos, K3PO4, tol-H2O, 100 °C

13D

[114]

Alkenyl and aryl Halides and triflates

n-alkylboronic acids

PdCl2(dppf),

K2CO3, Ag2O,

THF, 80 °C , 6–10 h

14A

[118]

Alkenyl halides

n-alkylboronic acids

PdCl(C3H5)dppb, Cs2CO3, toluene

14B

[119]

2-Bromoalken-3-ol derivatives

Primary and secondary alkylboronic acids

Pd(OAc)2,LBPhos.HBFK2CO3, toluene, 110 °C , 3–27 h

14C

[120]

Di-ortho-substituted arylhalides

Cyclic secondary alkylboronic acids

Pd(OAc)2, AntPhos,

K3PO4, toluene, 110 °C , 12–24 h

14D

[121]

Aryl and alkenyl triflates

Acyclic secondary alkylboronic acids

[Pd(cinnamyl)Cl]₂, Ligand, K3PO4.H2O,

toluene, 110 °C , 12 h

14E

[122]

Aryl methyl ethers bearing ortho-carbonyls

Boronic esters

RuH2(CO)(PPh3)3, toluene, 110 ^◦C

16A

[123]

Aryl and heteroarylbromides

MIDA boronates

PdCl2(dppf).CH2Cl2, Cs2CO3, THF:H₂O, 80 ^◦C, 24–48 h

17

[47]

Alkenyl bromide

Alkyl iodide and 9-MeO-9BBN (tBuLi for in situ generation)

Pd(OAc)₂, Aphos-Y

18B

[133]

Aryl bromide

OBBD derivatives

Pd(dtbpf)Cl_2, Et3N or K3PO4, TPGS-750-M/H2O 45 °C ,

Ar, 16–21 h

18D

[134]

Styrene

9-BBN

THF, SPhos and Pd(OAc)2 at 50 °C, 24 h

9

[97]

Aldehydes/ketones

Benzyl Trifluoroborates

4Cz-IPN, r.t. DMSO

12

[108]

Allyl bromides

Arylboronic acids

S-Catalyst and weak base

15

[122]