Ni-catalyzed Hydroalkylation of Olefins with N-sulfonyl Amines

Overview

Journal Nat Commun

Specialty Biology

Date 2021 Oct 8

PMID 34620857

Citations 5

Authors

Xiao-Biao Yan

Lun Li

Wen-Qiang Wu

Lun Xu

Ke Li

Yu-Cheng Liu

Hang Shi

Affiliations

Soon will be listed here.

Abstract

Hydroalkylation, the direct addition of a C(sp)-H bond across an olefin, is a desirable strategy to produce valuable, complex structural motifs in functional materials, pharmaceuticals, and natural products. Herein, we report a reliable method for accessing α-branched amines via nickel-catalyzed hydroalkylation reactions. Specifically, by using bis(cyclooctadiene)nickel (Ni(cod)) together with a phosphine ligand, we achieved a formal C(sp)-H bond insertion reaction between olefins and N-sulfonyl amines without the need for an external hydride source. The amine not only provides the alkyl motif but also delivers hydride to the olefin by means of a nickel-engaged β-hydride elimination/reductive elimination process. This method provides a platform for constructing chiral α-branched amines by using a P-chiral ligand, demonstrating its potential utility in organic synthesis. Notably, a sulfonamidyl boronate complex formed in situ under basic conditions promotes ring-opening of the azanickellacycle reaction intermediate, leading to a significant improvement of the catalytic efficiency.

Citing Articles

Hydroalkylation of unactivated olefins with C(sp)─H compounds enabled by NiH-catalyzed radical relay.

Shi J, Wang Y, Han Y, Chen J, Pu X, Xia Y Sci Adv. 2024; 10(51):eads6885.

PMID: 39693419 PMC: 11654677. DOI: 10.1126/sciadv.ads6885.

Enantioselective Metal-Catalyzed Reductive Coupling of Alkynes with Carbonyl Compounds and Imines: Convergent Construction of Allylic Alcohols and Amines.

Ortiz E, Shezaf J, Chang Y, Krische M ACS Catal. 2023; 12(14):8164-8174.

PMID: 37082110 PMC: 10112658. DOI: 10.1021/acscatal.2c02444.

Ni-catalyzed arylation of alkynes with organoboronic acids and aldehydes to access stereodefined allylic alcohols.

Tao S, Meng F, Wang T, Zheng Y Chem Sci. 2023; 14(8):2040-2045.

PMID: 36845934 PMC: 9945163. DOI: 10.1039/d2sc05894d.

Iron-Catalyzed Oxidative α-Amination of Ketones with Primary and Secondary Sulfonamides.

Song F, Park S, Wu C, Strom A J Org Chem. 2023; 88(5):3353-3358.

PMID: 36811395 PMC: 9990065. DOI: 10.1021/acs.joc.3c00210.

Regio-, Diastereo-, and Enantioselective Decarboxylative Hydroaminoalkylation of Dienol Ethers Enabled by Dual Palladium/Photoredox Catalysis.

Zheng J, Tang N, Xie H, Breit B Angew Chem Int Ed Engl. 2022; 61(20):e202200105.

PMID: 35170841 PMC: 9314026. DOI: 10.1002/anie.202200105.

References

Kubiak R, Prochnow I, Doye S . [Ind2TiMe2]: a catalyst for the hydroaminomethylation of alkenes and styrenes. Angew Chem Int Ed Engl. 2010; 49(14):2626-9. DOI: 10.1002/anie.200906557. View

Chen Y, Shuai B, Xu X, Li Y, Yang Q, Qiu H . Nickel-catalyzed Enantioselective Hydroarylation and Hydroalkenylation of Styrenes. J Am Chem Soc. 2019; 141(8):3395-3399. DOI: 10.1021/jacs.8b13524. View

Bielefeld J, Doye S . Fast Titanium-Catalyzed Hydroaminomethylation of Alkenes and the Formal Conversion of Methylamine. Angew Chem Int Ed Engl. 2020; 59(15):6138-6143. PMC: 7187458. DOI: 10.1002/anie.202001111. View

Jackson E, Malik H, Sormunen G, Baxter R, Liu P, Wang H . Mechanistic Basis for Regioselection and Regiodivergence in Nickel-Catalyzed Reductive Couplings. Acc Chem Res. 2015; 48(6):1736-45. PMC: 4470851. DOI: 10.1021/acs.accounts.5b00096. View

Saper N, Ohgi A, Small D, Semba K, Nakao Y, Hartwig J . Nickel-catalysed anti-Markovnikov hydroarylation of unactivated alkenes with unactivated arenes facilitated by non-covalent interactions. Nat Chem. 2020; 12(3):276-283. PMC: 11723504. DOI: 10.1038/s41557-019-0409-4. View

Thomas A, Denmark S . Pre-transmetalation intermediates in the Suzuki-Miyaura reaction revealed: The missing link. Science. 2016; 352(6283):329-32. DOI: 10.1126/science.aad6981. View

Matos K, Soderquist J . Alkylboranes in the Suzuki-Miyaura Coupling: Stereochemical and Mechanistic Studies. J Org Chem. 2001; 63(3):461-470. DOI: 10.1021/jo971681s. View

Yao W, Li R, Chen H, Chen M, Luan Y, Wang Y . Ni-catalyzed hydroaminoalkylation of alkynes with amines. Nat Commun. 2021; 12(1):3800. PMC: 8217523. DOI: 10.1038/s41467-021-24032-9. View

Xu G, Senanayake C, Tang W . P-Chiral Phosphorus Ligands Based on a 2,3-Dihydrobenzo[ d][1,3]oxaphosphole Motif for Asymmetric Catalysis. Acc Chem Res. 2019; 52(4):1101-1112. DOI: 10.1021/acs.accounts.9b00029. View

10.

Okumura S, Tang S, Saito T, Semba K, Sakaki S, Nakao Y . para-Selective Alkylation of Benzamides and Aromatic Ketones by Cooperative Nickel/Aluminum Catalysis. J Am Chem Soc. 2016; 138(44):14699-14704. DOI: 10.1021/jacs.6b08767. View

11.

Xiao L, Zhao C, Cheng L, Feng B, Feng W, Xie J . Nickel(0)-Catalyzed Hydroalkenylation of Imines with Styrene and Its Derivatives. Angew Chem Int Ed Engl. 2018; 57(13):3396-3400. DOI: 10.1002/anie.201713333. View

12.

Koperniku A, Foth P, Sammis G, Schafer L . Zirconium Hydroaminoalkylation. An Alternative Disconnection for the Catalytic Synthesis of α-Arylated Primary Amines. J Am Chem Soc. 2019; 141(48):18944-18948. DOI: 10.1021/jacs.9b10465. View

13.

Diesel J, Finogenova A, Cramer N . Nickel-Catalyzed Enantioselective Pyridone C-H Functionalizations Enabled by a Bulky N-Heterocyclic Carbene Ligand. J Am Chem Soc. 2018; 140(13):4489-4493. DOI: 10.1021/jacs.8b01181. View

14.

Wang Z, Yin H, Fu G . Catalytic enantioconvergent coupling of secondary and tertiary electrophiles with olefins. Nature. 2018; 563(7731):379-383. PMC: 6296363. DOI: 10.1038/s41586-018-0669-y. View

15.

He S, Wang J, Li Y, Xu Z, Wang X, Lu X . Nickel-Catalyzed Enantioconvergent Reductive Hydroalkylation of Olefins with α-Heteroatom Phosphorus or Sulfur Alkyl Electrophiles. J Am Chem Soc. 2019; 142(1):214-221. DOI: 10.1021/jacs.9b09415. View

16.

McDonald R, Liu G, Stahl S . Palladium(II)-catalyzed alkene functionalization via nucleopalladation: stereochemical pathways and enantioselective catalytic applications. Chem Rev. 2011; 111(4):2981-3019. PMC: 3076534. DOI: 10.1021/cr100371y. View

17.

Holmes M, Schwartz L, Krische M . Intermolecular Metal-Catalyzed Reductive Coupling of Dienes, Allenes, and Enynes with Carbonyl Compounds and Imines. Chem Rev. 2018; 118(12):6026-6052. PMC: 6203947. DOI: 10.1021/acs.chemrev.8b00213. View

18.

Jenkins A, Herath A, Song M, Montgomery J . Synthesis of cyclopentenols and cyclopentenones via nickel-catalyzed reductive cycloaddition. J Am Chem Soc. 2011; 133(36):14460-6. DOI: 10.1021/ja206722t. View

19.

Bair J, Schramm Y, Sergeev A, Clot E, Eisenstein O, Hartwig J . Linear-selective hydroarylation of unactivated terminal and internal olefins with trifluoromethyl-substituted arenes. J Am Chem Soc. 2014; 136(38):13098-101. DOI: 10.1021/ja505579f. View

20.

Ohashi M, Kishizaki O, Ikeda H, Ogoshi S . Ni(0)-catalyzed formation of azaaluminacyclopentenes via azanickelacyclopentenes: a unique nickel/aluminum double transmetalation reaction. J Am Chem Soc. 2009; 131(26):9160-1. DOI: 10.1021/ja903175g. View