Efficient Cobalt Catalyst for Ambient-Temperature Nitrile Dihydroboration, the Elucidation of a Chelate-Assisted Borylation Mechanism, and a New Synthetic Route to Amides

Chandrani Ghosh, Suyeon Kim, Matthew R. Mena, Jun Hyeong Kim, Raja Pal, Christopher L. Rock, Thomas L. Groy, Mu Hyun Baik, Ryan J. Trovitch

Research output: Contribution to journalArticle

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Abstract

N,N-Diborylamines have emerged as promising reagents in organic synthesis; however, their efficient preparation and full synthetic utility have yet to be realized. To address both shortcomings, an effective catalyst for nitrile dihydroboration was sought. Heating CoCl2 in the presence of PyEtPDI afforded the six-coordinate Co(II) salt, [(PyEtPDI)CoCl][Cl]. Upon adding 2 equiv of NaEt3BH, hydride transfer to one chelate imine functionality was observed, resulting in the formation of (κ4-N,N,N,N-PyEtIPCHMeNEtPy)Co. Single-crystal X-ray diffraction and density functional theory calculations revealed that this compound possesses a low-spin Co(II) ground state featuring antiferromagnetic coupling to a singly reduced imino(pyridine) moiety. Importantly, (κ4-N,N,N,N-PyEtIPCHMeNEtPy)Co was found to catalyze the dihydroboration of nitriles using HBPin with turnover frequencies of up to 380 h-1 at ambient temperature. Stoichiometric addition experiments revealed that HBPin adds across the Co-Namide bond to generate a hydride intermediate that can react with additional HBPin or nitriles. Computational evaluation of the reaction coordinate revealed that the B-H addition and nitrile insertion steps occur on the antiferromagnetically coupled triplet spin manifold. Interestingly, formation of the borylimine intermediate was found to occur following BPin transfer from the borylated chelate arm to regenerate (κ4-N,N,N,N-PyEtIPCHMeNEtPy)Co. Borylimine reduction is in turn facile and follows the same ligand-assisted borylation pathway. The independent hydroboration of alkyl and aryl imines was also demonstrated at 25 °C. With a series of N,N-diborylamines in hand, their addition to carboxylic acids allowed for the direct synthesis of amides at 120 °C, without the need for an exogenous coupling reagent.

Original languageEnglish
Pages (from-to)15327-15337
Number of pages11
JournalJournal of the American Chemical Society
Volume141
Issue number38
DOIs
Publication statusPublished - Sep 25 2019

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Nitriles
Cobalt
Amides
Hydrides
Catalysts
Temperature
Imines
Carboxylic acids
Pyridine
Ground state
Density functional theory
Ligands
Single crystals
Salts
Heating
Synthetic Chemistry Techniques
X ray diffraction
Carboxylic Acids
X-Ray Diffraction
Arm

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Efficient Cobalt Catalyst for Ambient-Temperature Nitrile Dihydroboration, the Elucidation of a Chelate-Assisted Borylation Mechanism, and a New Synthetic Route to Amides. / Ghosh, Chandrani; Kim, Suyeon; Mena, Matthew R.; Kim, Jun Hyeong; Pal, Raja; Rock, Christopher L.; Groy, Thomas L.; Baik, Mu Hyun; Trovitch, Ryan J.

In: Journal of the American Chemical Society, Vol. 141, No. 38, 25.09.2019, p. 15327-15337.

Research output: Contribution to journalArticle

Ghosh, Chandrani ; Kim, Suyeon ; Mena, Matthew R. ; Kim, Jun Hyeong ; Pal, Raja ; Rock, Christopher L. ; Groy, Thomas L. ; Baik, Mu Hyun ; Trovitch, Ryan J. / Efficient Cobalt Catalyst for Ambient-Temperature Nitrile Dihydroboration, the Elucidation of a Chelate-Assisted Borylation Mechanism, and a New Synthetic Route to Amides. In: Journal of the American Chemical Society. 2019 ; Vol. 141, No. 38. pp. 15327-15337.
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abstract = "N,N-Diborylamines have emerged as promising reagents in organic synthesis; however, their efficient preparation and full synthetic utility have yet to be realized. To address both shortcomings, an effective catalyst for nitrile dihydroboration was sought. Heating CoCl2 in the presence of PyEtPDI afforded the six-coordinate Co(II) salt, [(PyEtPDI)CoCl][Cl]. Upon adding 2 equiv of NaEt3BH, hydride transfer to one chelate imine functionality was observed, resulting in the formation of (κ4-N,N,N,N-PyEtIPCHMeNEtPy)Co. Single-crystal X-ray diffraction and density functional theory calculations revealed that this compound possesses a low-spin Co(II) ground state featuring antiferromagnetic coupling to a singly reduced imino(pyridine) moiety. Importantly, (κ4-N,N,N,N-PyEtIPCHMeNEtPy)Co was found to catalyze the dihydroboration of nitriles using HBPin with turnover frequencies of up to 380 h-1 at ambient temperature. Stoichiometric addition experiments revealed that HBPin adds across the Co-Namide bond to generate a hydride intermediate that can react with additional HBPin or nitriles. Computational evaluation of the reaction coordinate revealed that the B-H addition and nitrile insertion steps occur on the antiferromagnetically coupled triplet spin manifold. Interestingly, formation of the borylimine intermediate was found to occur following BPin transfer from the borylated chelate arm to regenerate (κ4-N,N,N,N-PyEtIPCHMeNEtPy)Co. Borylimine reduction is in turn facile and follows the same ligand-assisted borylation pathway. The independent hydroboration of alkyl and aryl imines was also demonstrated at 25 °C. With a series of N,N-diborylamines in hand, their addition to carboxylic acids allowed for the direct synthesis of amides at 120 °C, without the need for an exogenous coupling reagent.",
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T1 - Efficient Cobalt Catalyst for Ambient-Temperature Nitrile Dihydroboration, the Elucidation of a Chelate-Assisted Borylation Mechanism, and a New Synthetic Route to Amides

AU - Ghosh, Chandrani

AU - Kim, Suyeon

AU - Mena, Matthew R.

AU - Kim, Jun Hyeong

AU - Pal, Raja

AU - Rock, Christopher L.

AU - Groy, Thomas L.

AU - Baik, Mu Hyun

AU - Trovitch, Ryan J.

PY - 2019/9/25

Y1 - 2019/9/25

N2 - N,N-Diborylamines have emerged as promising reagents in organic synthesis; however, their efficient preparation and full synthetic utility have yet to be realized. To address both shortcomings, an effective catalyst for nitrile dihydroboration was sought. Heating CoCl2 in the presence of PyEtPDI afforded the six-coordinate Co(II) salt, [(PyEtPDI)CoCl][Cl]. Upon adding 2 equiv of NaEt3BH, hydride transfer to one chelate imine functionality was observed, resulting in the formation of (κ4-N,N,N,N-PyEtIPCHMeNEtPy)Co. Single-crystal X-ray diffraction and density functional theory calculations revealed that this compound possesses a low-spin Co(II) ground state featuring antiferromagnetic coupling to a singly reduced imino(pyridine) moiety. Importantly, (κ4-N,N,N,N-PyEtIPCHMeNEtPy)Co was found to catalyze the dihydroboration of nitriles using HBPin with turnover frequencies of up to 380 h-1 at ambient temperature. Stoichiometric addition experiments revealed that HBPin adds across the Co-Namide bond to generate a hydride intermediate that can react with additional HBPin or nitriles. Computational evaluation of the reaction coordinate revealed that the B-H addition and nitrile insertion steps occur on the antiferromagnetically coupled triplet spin manifold. Interestingly, formation of the borylimine intermediate was found to occur following BPin transfer from the borylated chelate arm to regenerate (κ4-N,N,N,N-PyEtIPCHMeNEtPy)Co. Borylimine reduction is in turn facile and follows the same ligand-assisted borylation pathway. The independent hydroboration of alkyl and aryl imines was also demonstrated at 25 °C. With a series of N,N-diborylamines in hand, their addition to carboxylic acids allowed for the direct synthesis of amides at 120 °C, without the need for an exogenous coupling reagent.

AB - N,N-Diborylamines have emerged as promising reagents in organic synthesis; however, their efficient preparation and full synthetic utility have yet to be realized. To address both shortcomings, an effective catalyst for nitrile dihydroboration was sought. Heating CoCl2 in the presence of PyEtPDI afforded the six-coordinate Co(II) salt, [(PyEtPDI)CoCl][Cl]. Upon adding 2 equiv of NaEt3BH, hydride transfer to one chelate imine functionality was observed, resulting in the formation of (κ4-N,N,N,N-PyEtIPCHMeNEtPy)Co. Single-crystal X-ray diffraction and density functional theory calculations revealed that this compound possesses a low-spin Co(II) ground state featuring antiferromagnetic coupling to a singly reduced imino(pyridine) moiety. Importantly, (κ4-N,N,N,N-PyEtIPCHMeNEtPy)Co was found to catalyze the dihydroboration of nitriles using HBPin with turnover frequencies of up to 380 h-1 at ambient temperature. Stoichiometric addition experiments revealed that HBPin adds across the Co-Namide bond to generate a hydride intermediate that can react with additional HBPin or nitriles. Computational evaluation of the reaction coordinate revealed that the B-H addition and nitrile insertion steps occur on the antiferromagnetically coupled triplet spin manifold. Interestingly, formation of the borylimine intermediate was found to occur following BPin transfer from the borylated chelate arm to regenerate (κ4-N,N,N,N-PyEtIPCHMeNEtPy)Co. Borylimine reduction is in turn facile and follows the same ligand-assisted borylation pathway. The independent hydroboration of alkyl and aryl imines was also demonstrated at 25 °C. With a series of N,N-diborylamines in hand, their addition to carboxylic acids allowed for the direct synthesis of amides at 120 °C, without the need for an exogenous coupling reagent.

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