Synthesis and some reactions of 3-amino-o-carboranes

Zakharkin, L. I.; Калинин, В. Н.; Gedymin, V. V.

doi:10.1016/s0022-328x(00)89762-4

Cited by 74 publications

(29 citation statements)

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“…[8,32,33] Their investigation dates back to the 1960s with the preparation of 1-H 2 N-1,2-closo-C 2 B 10 H 11 , [34] 3-Et 2 N-1,2-closo-C 2 B 10 H 11 , [35] and 3-H 2 N-1,2-closo-C 2 B 10 H 11 . [36] Carboranes containing two amino groups are far less studied and only 1,7-(H 2 N) 2--1,7-closo-C 2 B 10 H 10 and 1,12-(H 2 N) 2 -1,12-closo-C 2 B 10 H 10 were described, whereas the 1,2-isomer was reported to be less stable. [37,38] The applications of their derivatives are often similar to those of the isoelectronic closo-borates.…”

Section: Salts Of the [1-h 2 N-closo-cb 11 H 11 ]mentioning

confidence: 99%

Synthesis and Characterization of 2‐Mono‐ and 1,2‐Diaminocarba‐closo‐dodecaborates M[1‐R‐2‐H₂N‐closo‐CB₁₁H₁₀] (R=H, Ph, H₂N, CyHN)

Finze

2009

Chemistry A European J

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The first primary 2-aminocarba-closo-dodecaborates [1-R-2-H(2)N-closo-CB(11)H(10)](-) (R=H (1), Ph (2)) have been synthesized by insertion reactions of (Me(3)Si)(2)NBCl(2) into the trianions [7-R-7-nido-CB(10)H(10)](3-). The difunctionalized species [1,2-(H(2)N)(2)-closo-CB(11)H(10)] (3) and 1-CyHN-2-H(3)N-closo-CB(11)H(10) (H-4) have been prepared analogously from (Me(3)Si)(2)NBCl(2) and 7-H(3)N-7-nido-CB(10)H(12). In addition, the preparation of [Et(4)N][1-H(2)N-2-Ph-closo-CB(11)H(10)] ([Et(4)N]-5) starting from PhBCl(2) and 7-H(3)N-7-nido-CB(10)H(12) is described. Methylation of the [1-Ph-2-H(2)N-closo-CB(11)H(10)](-) ion (2) to produce 1-Ph-2-Me(3)N-closo-CB(11)H(10) (6) is reported. The crystal structures of [Et(4)N]-2, [Et(4)N]-5, and 6 were determined and the geometric parameters were compared to theoretical values derived from DFT and ab initio calculations. All new compounds were studied by NMR, IR, and Raman spectroscopy, MALDI mass spectrometry, and elemental analysis. The discussion of the experimental NMR chemical shifts and of selected vibrational band positions is supported by theoretical data. The thermal properties were investigated by differential scanning calorimetry (DSC). The pK(a) values of 2-H(3)N-closo-CB(11)H(11) (H-1), 1-H(3)N-closo-CB(11)H(10) (H-7), and 1,2-(H(3)N)(2)-closo-CB(11)H(10) (H(2)-3) were determined by potentiometric titration and by NMR studies. The experimental results are compared to theoretical data (DFT and ab initio). The basicities of the aminocarba-closo-dodecaborates agree well with the spectroscopic and structural properties.

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Section: Salts Of the [1-h 2 N-closo-cb 11 H 11 ]mentioning

confidence: 99%

Synthesis and Characterization of 2‐Mono‐ and 1,2‐Diaminocarba‐closo‐dodecaborates M[1‐R‐2‐H₂N‐closo‐CB₁₁H₁₀] (R=H, Ph, H₂N, CyHN)

Finze

2009

Chemistry A European J

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“…3-Diazonium-o-carborane tetrafluoroborate (1) was prepared in 70 % yield upon isolation, by treatment of 3-aminoo-carborane [12] with 1.2 equivalents of in situ generated nitrosyl fluoride in the presence of boron trifluoride. [13] It was noted that the stability of 1 is dependent upon the counterion used and BF 4 À offers the highest thermal stability of the salt among the anions, such as PF 6 À and Cl À , examined.…”

mentioning

confidence: 99%

1,3‐Dehydro‐o‐Carborane: Generation and Reaction with Arenes

2014

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Like the importance of benzyne, witnessed in modern arene chemistry for decades, 1,2-dehydro-o-carborane (o-carboryne), a three-dimensional relative of benzyne, has been used as a synthon for generating a wide range of cage, carbon-functionalized carboranes over the past 20 years. However, the selective B functionalization of the cage still represents a challenging task. Disclosed herein is the first example of 1,3-dehydro-o-carborane featuring a cage C-B bond having multiple bonding characters, and is successfully generated by treatment of 3-diazonium-o-carborane tetrafluoroborate with non-nucleophilic bases. This presents a new methodology for simultaneous functionalization of both cage carbon and boron vertices.

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“…Carboranyl amino acids were synthesized starting from readily available 3-amino-o-carborane (1) and its 1-R-substituted derivatives (2, R = Me; 3, R = Ph) [6].…”

Section: Resultsmentioning

confidence: 99%

“…All signals are expressed in ppm (d). Acylated amino derivatives 4-10 were prepared according to the literature procedures [6,8].…”

Section: Generalmentioning

confidence: 99%

Synthesis of carborane analogues of γ-aminobutanoic acid

Ol’shevskaya

Ayuob

Brechko

et al. 2005

Journal of Organometallic Chemistry

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Synthesis and some reactions of 3-amino-o-carboranes

Cited by 74 publications

References 1 publication

Synthesis and Characterization of 2‐Mono‐ and 1,2‐Diaminocarba‐closo‐dodecaborates M[1‐R‐2‐H₂N‐closo‐CB₁₁H₁₀] (R=H, Ph, H₂N, CyHN)

Synthesis and Characterization of 2‐Mono‐ and 1,2‐Diaminocarba‐closo‐dodecaborates M[1‐R‐2‐H₂N‐closo‐CB₁₁H₁₀] (R=H, Ph, H₂N, CyHN)

1,3‐Dehydro‐o‐Carborane: Generation and Reaction with Arenes

Synthesis of carborane analogues of γ-aminobutanoic acid

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Synthesis and some reactions of 3-amino-o-carboranes

Cited by 74 publications

References 1 publication

Synthesis and Characterization of 2‐Mono‐ and 1,2‐Diaminocarba‐closo‐dodecaborates M[1‐R‐2‐H2N‐closo‐CB11H10] (R=H, Ph, H2N, CyHN)

Synthesis and Characterization of 2‐Mono‐ and 1,2‐Diaminocarba‐closo‐dodecaborates M[1‐R‐2‐H2N‐closo‐CB11H10] (R=H, Ph, H2N, CyHN)

1,3‐Dehydro‐o‐Carborane: Generation and Reaction with Arenes

Synthesis of carborane analogues of γ-aminobutanoic acid

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Synthesis and Characterization of 2‐Mono‐ and 1,2‐Diaminocarba‐closo‐dodecaborates M[1‐R‐2‐H₂N‐closo‐CB₁₁H₁₀] (R=H, Ph, H₂N, CyHN)

Synthesis and Characterization of 2‐Mono‐ and 1,2‐Diaminocarba‐closo‐dodecaborates M[1‐R‐2‐H₂N‐closo‐CB₁₁H₁₀] (R=H, Ph, H₂N, CyHN)