The Coupling of Aryl Grignard Reagents to Benzyl Systems

Vingiello, Frank A.; Quo, Sih-Gwan; Sheridan, J.

doi:10.1021/jo01067a040

Cited by 20 publications

(9 citation statements)

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“…Vingiello synthesized diarylmethanes via a simple substitution reaction of benzylic chlorides with aryl Grignard reagents. 3 FriedelCrafts alkylation between various benzyl donors and aryl nucleophiles has also been applied to the synthesis of diarylmethanes. 4 More recently, transition metals such as copper, 5 palladium, 6 and nickel 7 have been found to enhance the synthetic utility of cross-coupling reactions that afford diarylmethanes.…”

mentioning

confidence: 99%

Ligand-controlled Iron-catalyzed Cross Coupling of Benzylic Chlorides with Aryl Grignard Reagents

Kawamura

Nakamura

2013

Chemistry Letters

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The selective cross coupling of benzylic chlorides with aryl Grignard reagents has been achieved by using catalytic amounts of FeCl2 and electronically tuned ortho-phenylenebisphosphine ligands. Although electron-deficient ligands promoted the reductive homocoupling of benzylic halides, electron-rich ligands effectively promoted the desired cross-coupling reaction to afford the corresponding diarylmethanes in good to excellent yields.

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mentioning

confidence: 99%

Ligand-controlled Iron-catalyzed Cross Coupling of Benzylic Chlorides with Aryl Grignard Reagents

Kawamura

Nakamura

2013

Chemistry Letters

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“…The absolute structure of the molecule was reliably determined. Using the program Platon [5] the refined structure was calculated to have a Flack parameter of -0.012 (16), a Parsons parameter of -0.003( 16) and a Hooft parameter of 0.012 (15). These values agree with the Parson's value calculated by the program SHELXL, -0.012(16) from 3921 selected quotients.…”

Section: Compound 14a (Major Product)mentioning

confidence: 52%

“…We decided to prepare a Bradsher cyclization substrate via direct alkylation of the Grignard reagent derived from commercially available bromoacetal 7b with thienylmethyl bromide 10a, rather than making 7a (Scheme 3, equation 1). 16 Bromide 10a is accessible in 1 step from commercial flavoring ingredient thienylmethanol 9a. 17 and magnesium turnings.…”

Section: Scheme 3 Realized Bradsher Routes To Naphthothiophene and 3-bromonaphthothiophenementioning

confidence: 99%

Efficient Synthesis and Functionalization of 3-Bromo Naphtho[2,3b]thiophene

Burke

Welsh

Robertson³

et al. 2021

Preprint

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Naphtho[2,3b]thiophene is a linear sulfur containing polycyclic aromatic hydrocarbon. Naphtho[2,3b]thiophene and its derivatives are commonly accessed by a Bradsher cyclization. Synthesis of the Bradsher cyclization substrate typically requires harsh conditions, including several oxidation state changes. Here we report an improved, multigram synthesis of 3-bromonaphtho[2,3b]thiophene, exploiting a copper-catalyzed cross coupling to prepare the Bradsher substrate in 3 steps from commercial materials while minimizing redox reactions. Modification of the naphthothiophene scaffold in the 3-position has not previously been reported. In this work, the 3-bromonaphthothiophene is further functionalized via lithium-halogen exchange, with the key finding being a specific order of addition in lithiation is required to avoid undesired rearrangement reactions. A small yet versatile set of derivatives, including a naphthothiophene-containing chiral amine are prepared.

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“…23 We sought to prepare the Bradsher cyclization substrate by alkylation of a Grignard reagent derived from commercially available bromoacetal 11a with thienylmethyl bromide 12a. 24 Bromide 12a is accessible in 1 step from commercial flavoring ingredient thienylmethanol 12b.…”

Section: Scheme 3 Magnesium Thiolate/benzyne Route To 2amentioning

confidence: 99%

Short Syntheses of 1-Substituted Dibenzothiophenes and 3-Substituted Naphthothiophenes

Welsh¹,

Burke²,

Robertson³

et al. 2019

Preprint

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<p>The 1-substituted dibenzothiophene motif is an unusual substitution pattern. We demonstrate a simple one-pot preparation of 1-lithiodibenzothiophene via a cascade of two benzyne additions and conversion to the aldehyde, boronic ester, and iodide. This work avoids the use of precious metals or tert-butyllithium and is shorter than existing routes to these compounds. We also report an improved route to the isomeric 3-substituted naphthothiophene scaffold. These protocols will allow rapid access to families of these two related heteroacenes.</p>

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The Coupling of Aryl Grignard Reagents to Benzyl Systems

Cited by 20 publications

References 0 publications

Ligand-controlled Iron-catalyzed Cross Coupling of Benzylic Chlorides with Aryl Grignard Reagents

Ligand-controlled Iron-catalyzed Cross Coupling of Benzylic Chlorides with Aryl Grignard Reagents

Efficient Synthesis and Functionalization of 3-Bromo Naphtho[2,3b]thiophene

Short Syntheses of 1-Substituted Dibenzothiophenes and 3-Substituted Naphthothiophenes

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