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Volumn 2, Issue 9, 2011, Pages 1766-1771

Nickel-catalyzed amination of aryl carbamates and sequential site-selective cross-couplings

Author keywords

[No Author keywords available]

Indexed keywords

CATALYTIC CYCLES; COMPUTATIONAL STUDIES; CROSS-COUPLINGS; FUNCTIONALIZATIONS; RATE DETERMINING STEP; REDUCTIVE ELIMINATION; SITE SELECTIVE;

EID: 81355149534     PISSN: 20416520     EISSN: 20416539     Source Type: Journal    
DOI: 10.1039/c1sc00230a     Document Type: Article
Times cited : (144)

References (81)
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    • The amination of aryl methyl ethers is largely limited to the coupling of 2-methoxynaphthalene with cyclic secondary amines. Deviation from these substrates leads to significantly lower yields (ca. 30-50%)
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    • Aryl N,N-diethylcarbamates are readily prepared from aryl alcohols and commercially available N,N-diethylcarbamoyl chloride. The latter reagent costs approximately $20-25 per mol ($0.15-$0.20 per gram) from common chemical suppliers, such as Alfa Aesar and Aldrich Chemical Co., Inc. Other phenol-based amination partners cannot be used effectively for directed metallation/functionalization. Specifically, aryl sulfonates and pivalates are not suitable substrates, whereas aryl methyl ethers are poor metalation substrates. Aryl sulfamates can be used in ortho-lithiation, but the sulfamate directing group ability is approximately 20x less compared to carbamates; see ref. 13f
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    • All geometries were optimized using the B3LYP functional and a mixed basis set of SDD for Ni and 631G(d) for other atoms. A larger base set, SDD for Ni and 6-311 + G(2d, p) for other atoms was used for single point energy calculations and solvation energy corrections using the CPCM model. Single point calculations using the B3P86 and B3PW91 functionals were also performed and give comparable results to the B3LYP calculations (see ESI† for details) The isopropyl groups on the SIPr ligand were replaced with methyls in the calculations to reduce computational cost. All calculations were performed using Gaussian 09. Gaussian 09, revision B.01, Gaussian, Inc., Wallingford CT, The Ni-catalyzed amination of aryl carbamates is not inhibited in the presence of galvinoxyl radical or BHT; thus, we propose that a Ni(i)/Ni(iii) catalytic cycle is likely not operative. For examples where additives such as galvinoxyl radical or BHT are used to probe the presence of Ni(i) intermediates, see
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    • Since the mechanism involves charged species, the energetics of the deprotonation step is expected to be strongly affected by solvation effects. We have tested a number of DFT methods and basis sets with the CPCM solvation model. These results (provided in the ESI†) all indicate that deprotonation is not the rate-limiting step
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    • -1) between complex 5 at the beginning and end of the plot represents the energy released in the catalytic cycle. ref. 31 Competition experiments between phenol-derived carbamates and sulfamates indicate that sulfamates are inherently more reactive than carbamates in both the nickel-catalyzed Suzuki-Miyaura coupling and amination. The preference for sulfamate coupling seen in the conversion of 18 → 20 is likely heightened because of the carbamate's ortho substituent
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* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.