Copper‐Catalyzed Electrophilic Amination of Heteroaromatic and Aromatic CH Bonds via
            <scp>TMPZnCl</scp>
            ·LiCl Mediated Metalation

McDonald, Shelley; Hendrick, Charles E.; Bitting, Katie J.; Wang, Qiu

doi:10.1002/0471264229.os092.27

Cited by 3 publications

(3 citation statements)

References 36 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The use of TMPZnCl•LiCl (80) is compatible with electrophilic aminations as shown by Wang. 48,49 Thus, TMPZnCl•LiCl (80) regioselectively zincates 3-fluoropyridine (49) at 25 °C. Addition of a Cu(II)-catalyst (5 mol% Cu(OAc) 2 ) at 50 °C for 18 h in the presence of the electrophilic amination reagent, a benzoyloxypiperazine derivative (98), provides the amination product 99 in 53% yield at a 60 mmol scale.…”

Section: Scheme 18 Metalation Of Azine N-oxides Using Tmpzncl•licl (80)mentioning

confidence: 99%

“…After Pd(0)-catalyzed cross-couplings, the desired arylated products of type 212 are obtained. Alternatively, the metalation of 210 with TMP 2 Zn•2LiCl•2MgCl 2 (49) As shown above, the presence or absence of a Lewis acid such as BF 3 •OEt 2 or MgCl 2 is essential for achieving a high regioselectivity in metalations with TMP-bases. This has been demonstrated for various heterocyclic metalations.…”

Section: Review Syn Openmentioning

confidence: 99%

See 1 more Smart Citation

Regioselective C–H Activation of Substituted Pyridines and other Azines using Mg- and Zn-TMP-Bases

Balkenhohl

Knöchel

2018

SynOpen

View full text Add to dashboard Cite

The metalation of substituted pyridines, diazines and related N-heterocycles using TMPMgCl·LiCl, TMP2Mg·2LiCl, TMPZnCl·LiCl or TMP2Zn·2LiCl2·2MgCl2 (TMP = 2,2,6,6-tetramethylpiperidyl) in the presence or absence of a Lewis acid is reviewed. Contents 1 Introduction2 Magnesiation of Pyridines and Related Azines2.1 Magnesiations using TMPMgCl·LiCl2.2 Magnesiations using TMP2Mg·2LiCl and Related Bases2.3 BF3·OEt2 Promoted Metalations of Pyridines3 Zincation of Pyridines and Related Azines using TMPZnCl·LiCl and TMP2Zn·2LiCl·2MgCl2 4 Metalation of Pyridines using other TMP-Bases5 Magnesiation and Zincation of Diazines6 Conclusion

show abstract

Section: Scheme 18 Metalation Of Azine N-oxides Using Tmpzncl•licl (80)mentioning

confidence: 99%

Section: Review Syn Openmentioning

confidence: 99%

Regioselective C–H Activation of Substituted Pyridines and other Azines using Mg- and Zn-TMP-Bases

Balkenhohl

Knöchel

2018

SynOpen

View full text Add to dashboard Cite

show abstract

“…Taking into account our preliminary results described in a previous communication, [42] as well as the literature data, [42][43][44] we have envisaged that the required chemo-and regioselectivity could be achieved via directed ortho metalation (DOM) of 2-or 3bromopyridines (Scheme 3). [45][46][47][48] The bromine atom might serve as the directed metalation group, which could be easily removed under reductive conditions. Other modifications necessary for the preparation of the title compounds included pyridine ring hydrogenation and deoxygenation; all the aforementioned transformations could be achieved under reductive reaction conditions.…”

Section: Introductionmentioning

confidence: 99%

Scalable and Straightforward Synthesis of All Isomeric (Cyclo)alkylpiperidines

et al. 2019

View full text Add to dashboard Cite

An efficient approach towards introducing (cyclo)alkyl substituents at C‐2, C‐3 or C‐4 positions of the piperidine ring was described. The method relied on the straightforward two‐step reaction sequence based on the formal sp3–sp3 retrosynthetic disconnection. The procedure commenced with selective directed ortho metalation of 2‐ and 3‐bromopyridine, followed by reaction with aldehydes or ketones. The optimized methods were developed for all three isomers of hydroxyalkyl‐substituted pyridines, which were synthesized in 28–84 % overall yield (20 examples). Catalytic hydrogenation of these adducts could be performed selectively with or without retention of the hydroxyl group in their molecules, so that either (cyclo)alkylpiperidines (14 examples) or the corresponding saturated amino alcohols (16 examples) were obtained (28–96 % and 82–96 % yield, respectively). After minor modifications, the developed method was also implemented in a flow reactor and a 5 L autoclave, which allowed for the preparation of up to 0.5 kg of the representative (cyclo)alkylpiperidines.

show abstract

Arylation, Vinylation, and Alkynylation of Electron-Deficient (Hetero)arenes Using Iodonium Salts

Liu

Wang

2016

Org. Lett.

Self Cite

View full text Add to dashboard Cite

Arylation, vinylation, and alkynylation of electron-deficient arenes and heteroarenes have been achieved by chemoselective C-H zincation followed by copper-catalyzed coupling reactions using iodonium salts. This approach offers a direct and general access to a wide scope of (hetero)biaryls as well as alkenylated and alkynylated heteroarenes under mild conditions. It is particularly useful and valuable for the rapid and modular synthesis of diverse (hetero)aryl compounds, as demonstrated in the synthesis of transient receptor potential vanilloid 1 (TRPV1) antagonists and angiotensin II receptor type 1 (AT1 receptor) antagonists.

show abstract

Copper‐Catalyzed Electrophilic Amination of Heteroaromatic and Aromatic CH Bonds via TMPZnCl ·LiCl Mediated Metalation

Cited by 3 publications

References 36 publications

Regioselective C–H Activation of Substituted Pyridines and other Azines using Mg- and Zn-TMP-Bases

Regioselective C–H Activation of Substituted Pyridines and other Azines using Mg- and Zn-TMP-Bases

Scalable and Straightforward Synthesis of All Isomeric (Cyclo)alkylpiperidines

Arylation, Vinylation, and Alkynylation of Electron-Deficient (Hetero)arenes Using Iodonium Salts

Contact Info

Product

Resources

About