Bifunctional Ligand Enables Efficient Gold-Catalyzed Hydroalkenylation of Propargylic Alcohol

Overview

Journal Angew Chem Int Ed Engl

Specialty Chemistry

Date 2018 Apr 29

PMID 29704310

Citations 8

Authors

Shengrong Liao

Alessio Porta

Xinpeng Cheng

Xu Ma

Giuseppe Zanoni

Liming Zhang

Affiliations

Soon will be listed here.

Abstract

Using the previously designed biphenyl-2-ylphosphine ligand, featuring a remote tertiary amino group, the first gold-catalyzed intermolecular hydroalkenylation of alkynes has been developed. Synthetically valuable conjugated dienyl alcohols are formed in moderate to good yields. A range of alkenyltrifluoroborates are allowed as the alkenyl donor, and no erosion of alkene geometry and/or the propargylic configuration are detected. DFT calculations confirm the critical role of the remote basic group in the ligand as a general-base catalyst for promoting this novel gold catalysis with good efficiency.

Citing Articles

A Chemoselective Polarity-Mismatched Photocatalytic C(sp )-C(sp ) Cross-Coupling Enabled by Synergistic Boron Activation.

Brals J, McGuire T, Watson A Angew Chem Int Ed Engl. 2023; 62(42):e202310462.

PMID: 37622419 PMC: 10952440. DOI: 10.1002/anie.202310462.

New-Generation Ligand Design for the Gold-Catalyzed Asymmetric Activation of Alkynes.

Zuccarello G, Escofet I, Caniparoli U, Echavarren A Chempluschem. 2021; 86(9):1283-1296.

PMID: 34472729 PMC: 8457203. DOI: 10.1002/cplu.202100232.

Au⋅⋅⋅H-C Hydrogen Bonds as Design Principle in Gold(I) Catalysis.

Darmandeh H, Loffler J, Tzouras N, Dereli B, Scherpf T, Feichtner K Angew Chem Int Ed Engl. 2021; 60(38):21014-21024.

PMID: 34313367 PMC: 8518757. DOI: 10.1002/anie.202108581.

Synthesis of Chiral Bifunctional NHC Ligands and Survey of Their Utilities in Asymmetric Gold Catalysis.

Zhang J, Liu Y, Wang X, Zhang L Organometallics. 2021; 38(20):3931-3938.

PMID: 34290468 PMC: 8290929. DOI: 10.1021/acs.organomet.9b00400.

Chiral Bifunctional Phosphine Ligand-Enabled Cooperative Cu Catalysis: Formation of Chiral α,β-Butenolides via Highly Enantioselective γ-Protonation.

Cheng X, Li T, Gutman K, Zhang L J Am Chem Soc. 2021; 143(29):10876-10881.

PMID: 34264076 PMC: 8648128. DOI: 10.1021/jacs.1c05781.

References

Sarkar S, Wanzala E, Shibahara S, Takahashi K, Ishihara J, Hatakeyama S . Enantio- and stereoselective route to the phoslactomycin family of antibiotics: formal synthesis of (+)-fostriecin and (+)-phoslactomycin B. Chem Commun (Camb). 2009; (39):5907-9. DOI: 10.1039/b912267b. View

Furstner A, Davies P . Catalytic carbophilic activation: catalysis by platinum and gold pi acids. Angew Chem Int Ed Engl. 2007; 46(19):3410-49. DOI: 10.1002/anie.200604335. View

Li Y, Han Y, Xiong H, Zhu N, Qian B, Ye C . Copper-Catalyzed Regioselective 1,2-Alkylesterification of Dienes to Allylic Esters. Org Lett. 2016; 18(3):392-5. DOI: 10.1021/acs.orglett.5b03399. View

Cheong P, Morganelli P, Luzung M, Houk K, Toste F . Gold-catalyzed cycloisomerization of 1,5-allenynes via dual activation of an ene reaction. J Am Chem Soc. 2008; 130(13):4517-26. PMC: 2995695. DOI: 10.1021/ja711058f. View

Jimenez-Nunez E, Echavarren A . Gold-catalyzed cycloisomerizations of enynes: a mechanistic perspective. Chem Rev. 2008; 108(8):3326-50. DOI: 10.1021/cr0684319. View

Molander G, Cadoret F . Synthesis of the stereogenic triad of the halicyclamine A core. Tetrahedron Lett. 2011; 52(17):2199-2202. PMC: 3079922. DOI: 10.1016/j.tetlet.2010.11.162. View

Huang Y, Yang X, Lv Z, Cai C, Kai C, Pei Y . Asymmetric Synthesis of 1,3-Butadienyl-2-carbinols by the Homoallenylboration of Aldehydes with a Chiral Phosphoric Acid Catalyst. Angew Chem Int Ed Engl. 2015; 54(25):7299-302. DOI: 10.1002/anie.201501832. View

Hayashi T, Inoue K, Taniguchi N, Ogasawara M . Rhodium-catalyzed hydroarylation of alkynes with arylboronic acids: 1,4-shift of rhodium from 2-aryl-1-alkenylrhodium to 2-alkenylarylrhodium intermediate. J Am Chem Soc. 2001; 123(40):9918-9. DOI: 10.1021/ja0165234. View

Zhang D, Tang X, Shi M . Gold-catalyzed tandem reactions of methylenecyclopropanes and vinylidenecyclopropanes. Acc Chem Res. 2013; 47(3):913-24. DOI: 10.1021/ar400159r. View

10.

Clark D, Clark J, Diver S . Alkenol-alkyne cross metathesis. Org Lett. 2008; 10(10):2055-8. DOI: 10.1021/ol800523j. View

11.

Oh C, Jung H, Kim K, Kim N . The palladium-catalyzed addition of organoboronic acids to alkynes. Angew Chem Int Ed Engl. 2003; 42(7):805-8. DOI: 10.1002/anie.200390214. View

12.

Li X, Liao S, Wang Z, Zhang L . Ligand-Accelerated Gold-Catalyzed Addition of in Situ Generated Hydrazoic Acid to Alkynes under Neat Conditions. Org Lett. 2017; 19(14):3687-3690. DOI: 10.1021/acs.orglett.7b01359. View

13.

White J, Choi Y . Catalyzed asymmetric diels-alder reaction of benzoquinone. Total synthesis of (-)-ibogamine. Org Lett. 2000; 2(15):2373-6. DOI: 10.1021/ol0001463. View

14.

Panteleev J, Huang R, Lui E, Lautens M . Addition of arylboronic acids to arylpropargyl alcohols en route to indenes and quinolines. Org Lett. 2011; 13(19):5314-7. DOI: 10.1021/ol202176g. View

15.

Hashmi A . Gold-catalyzed organic reactions. Chem Rev. 2007; 107(7):3180-211. DOI: 10.1021/cr000436x. View

16.

Zheng C, Wang D, Stahl S . Catalyst-controlled regioselectivity in the synthesis of branched conjugated dienes via aerobic oxidative Heck reactions. J Am Chem Soc. 2012; 134(40):16496-9. PMC: 3495987. DOI: 10.1021/ja307371w. View

17.

Lopez-Carrillo V, Echavarren A . Gold(I)-catalyzed intermolecular [2+2] cycloaddition of alkynes with alkenes. J Am Chem Soc. 2010; 132(27):9292-4. DOI: 10.1021/ja104177w. View

18.

Lin P, Jeganmohan M, Cheng C . Cobalt(II)-catalyzed regio- and stereoselective hydroarylation of alkynes with organoboronic acids. Chemistry. 2008; 14(36):11296-9. DOI: 10.1002/chem.200801858. View

19.

Clark J, French J, Jecs E, Diver S . Geminal alkene-alkyne cross metathesis using a relay strategy. Org Lett. 2012; 14(16):4178-81. DOI: 10.1021/ol301846q. View

20.

Naodovic M, Xia G, Yamamoto H . TBOxCr(III)Cl-catalyzed enantioselective synthesis of 1,3-butadien-2-ylcarbinols. Org Lett. 2008; 10(18):4053-5. DOI: 10.1021/ol801452c. View