NHC-Cu-catalyzed Addition of Propargylboron Reagents to Phosphinoylimines. Enantioselective Synthesis of Trimethylsilyl-substituted Homoallenylamides and Application to the Synthesis of S-(-)-cyclooroidin

Overview

Journal J Am Chem Soc

Publisher American Chemical Society

Specialty Chemistry

Date 2014 Feb 22

PMID 24555471

Citations 11

Authors

Nicholas W Mszar

Fredrik Haeffner

Amir H Hoveyda

Affiliations

Soon will be listed here.

Abstract

A catalytic method for the efficient and enantioselective addition of a 1-trimethylsilyl-substituted allene moiety to phosphinoylimines is presented. Transformations are promoted by 5.0 mol % of a copper complex of an N-heterocyclic carbene in the presence of a propargylboron reagent that can be readily prepared in multigram quantities. Within 10 min of reaction, products are obtained in up to 91% yield, 98% allene (vs propargyl) selectivity, and 98:2 enantiomeric ratio. An assortment of aldimines serve as suitable substrates. The phosphinoyl and silyl groups can be removed efficiently and orthogonally. The silylallene moiety may be transformed to versatile derivatives that are difficult to access via nonsilylated allenes. The special features and utility of the approach are highlighted through a succinct enantioselective synthesis of marine alkaloid S-(-)-cyclooroidin.

Citing Articles

Tailored chiral phosphoramidites support highly enantioselective Pd catalysts for asymmetric aminoalkylative amination.

Zou S, Zhao Z, Yang G, Huang H Nat Commun. 2024; 15(1):10477.

PMID: 39622821 PMC: 11612159. DOI: 10.1038/s41467-024-54328-5.

Synthesis of 1,4,5,6-tetrahydropyridazines and pyridazines transition-metal-free (4 + 2) cycloaddition of alkoxyallenes with 1,2-diaza-1,3-dienes.

Wu Q, Shao P, He Y RSC Adv. 2022; 9(37):21507-21512.

PMID: 35521294 PMC: 9066181. DOI: 10.1039/c9ra02712b.

Racemic Vinylallenes in Catalytic Enantioselective Multicomponent Processes: Rapid Generation of Complexity through 1,6-Conjugate Additions.

Huang Y, Torker S, Li X, Del Pozo J, Hoveyda A Angew Chem Int Ed Engl. 2019; 58(9):2685-2691.

PMID: 30653802 PMC: 6481603. DOI: 10.1002/anie.201812535.

Enantioselective Synthesis of Trisubstituted Allenyl-B(pin) Compounds by Phosphine-Cu-Catalyzed 1,3-Enyne Hydroboration. Insights Regarding Stereochemical Integrity of Cu-Allenyl Intermediates.

Huang Y, Del Pozo J, Torker S, Hoveyda A J Am Chem Soc. 2018; 140(7):2643-2655.

PMID: 29417810 PMC: 6019291. DOI: 10.1021/jacs.7b13296.

A Computational Investigation of the Ligand-Controlled Cu-Catalyzed Site-Selective Propargylation and Allenylation of Carbonyl Compounds.

Zou Y, Gutierrez O, Sader A, Patel N, Fandrick D, Busacca C Org Lett. 2017; 19(22):6064-6067.

PMID: 29095633 PMC: 5718194. DOI: 10.1021/acs.orglett.7b02845.

References

Hughes C, Kauffman C, Jensen P, Fenical W . Structures, reactivities, and antibiotic properties of the marinopyrroles A-F. J Org Chem. 2010; 75(10):3240-50. PMC: 2884375. DOI: 10.1021/jo1002054. View

Reddy L . Chiral Brønsted acid catalyzed enantioselective allenylation of aldehydes. Chem Commun (Camb). 2012; 48(73):9189-91. DOI: 10.1039/c2cc34371a. View

Gainer M, Bennett N, Takahashi Y, Looper R . Regioselective rhodium(II)-catalyzed hydroaminations of propargylguanidines. Angew Chem Int Ed Engl. 2011; 50(3):684-7. PMC: 3631534. DOI: 10.1002/anie.201006087. View

Vieira E, Snapper M, Hoveyda A . Enantioselective synthesis of homoallylic amines through reactions of (pinacolato)allylborons with aryl-, heteroaryl-, alkyl-, or alkene-substituted aldimines catalyzed by chiral C1-symmetric NHC-Cu complexes. J Am Chem Soc. 2011; 133(10):3332-5. PMC: 3059089. DOI: 10.1021/ja200311n. View

Ferretti C, Marengo B, Ciucis C, Nitti M, Pronzato M, Marinari U . Effects of Agelas oroides and Petrosia ficiformis crude extracts on human neuroblastoma cell survival. Int J Oncol. 2006; 30(1):161-9. View

Semba K, Shinomiya M, Fujihara T, Terao J, Tsuji Y . Highly selective copper-catalyzed hydroboration of allenes and 1,3-dienes. Chemistry. 2013; 19(22):7125-32. DOI: 10.1002/chem.201300443. View

Cowen B, Saunders L, Miller S . Pyridylalanine (pal)-peptide catalyzed enantioselective allenoate additions to N-acyl imines. J Am Chem Soc. 2009; 131(17):6105-7. DOI: 10.1021/ja901279m. View

Alcaide B, Almendros P, Aragoncillo C . Metal-promoted allylation, propargylation, or allenylation of azetidine-2,3-diones in aqueous and anhydrous media. Application to the asymmetric synthesis of densely functionalized 3-substituted 3-hydroxy-beta-lactams. J Org Chem. 2001; 66(15):5208-16. DOI: 10.1021/jo015704l. View

Meng F, Jung B, Haeffner F, Hoveyda A . NHC-Cu-catalyzed protoboration of monosubstituted allenes. Ligand-controlled site selectivity, application to synthesis and mechanism. Org Lett. 2013; 15(6):1414-7. PMC: 3625862. DOI: 10.1021/ol4004178. View

10.

Yu S, Ma S . Allenes in catalytic asymmetric synthesis and natural product syntheses. Angew Chem Int Ed Engl. 2012; 51(13):3074-112. DOI: 10.1002/anie.201101460. View

11.

Wisniewska H, Jarvo E . Enantioselective propargylation and allenylation reactions of ketones and imines. J Org Chem. 2013; 78(23):11629-36. DOI: 10.1021/jo4019107. View

12.

Mukherjee S, Sivappa R, Yousufuddin M, Lovely C . Asymmetric total synthesis of ent-cyclooroidin. Org Lett. 2010; 12(21):4940-3. PMC: 3099645. DOI: 10.1021/ol1020916. View

13.

Ermolatev D, Bariwal J, Steenackers H, de Keersmaecker S, Van der Eycken E . Concise and diversity-oriented route toward polysubstituted 2-aminoimidazole alkaloids and their analogues. Angew Chem Int Ed Engl. 2010; 49(49):9465-8. DOI: 10.1002/anie.201004256. View

14.

Guo L, Gao H, Mayer P, Knochel P . Preparation of organoaluminum reagents from propargylic bromides and aluminum activated by PbCl2 and their regio- and diastereoselective addition to carbonyl derivatives. Chemistry. 2010; 16(32):9829-34. DOI: 10.1002/chem.201000523. View

15.

Hashimoto T, Sakata K, Tamakuni F, Dutton M, Maruoka K . Phase-transfer-catalysed asymmetric synthesis of tetrasubstituted allenes. Nat Chem. 2013; 5(3):240-4. DOI: 10.1038/nchem.1567. View

16.

Burks H, Liu S, Morken J . Development, mechanism, and scope of the palladium-catalyzed enantioselective allene diboration. J Am Chem Soc. 2007; 129(28):8766-73. DOI: 10.1021/ja070572k. View

17.

Huang Y, Chakrabarti A, Morita N, Schneider U, Kobayashi S . A catalytic asymmetric borono variant of Hosomi-Sakurai reactions with N,O-aminals. Angew Chem Int Ed Engl. 2011; 50(47):11121-4. DOI: 10.1002/anie.201105182. View

18.

Movassaghi M, Siegel D, Han S . Total synthesis of all (-)-Agelastatin alkaloids. Chem Sci. 2011; 1:561-566. PMC: 3016719. DOI: 10.1039/c0sc00351d. View

19.

Hernandez E, Burgos C, Alicea E, Soderquist J . B-allenyl- and B-(gamma-trimethylsilylpropargyl)-10-phenyl-9-borabicyclo[3.3.2]decanes: asymmetric synthesis of propargyl and alpha-allenyl 3-degree-carbinols from ketones. Org Lett. 2006; 8(18):4089-91. PMC: 2597672. DOI: 10.1021/ol061596j. View

20.

Yus M, Gonzalez-Gomez J, Foubelo F . Catalytic enantioselective allylation of carbonyl compounds and imines. Chem Rev. 2011; 111(12):7774-854. DOI: 10.1021/cr1004474. View