Enantioselective Rhodium(III)-Catalyzed Markovnikov Hydroboration of Unactivated Terminal Alkenes

Overview

Journal J Am Chem Soc

Publisher American Chemical Society

Specialty Chemistry

Date 2017 Jul 1

PMID 28665124

Citations 20

Authors

James R Smith

Beatrice S L Collins

Matthew J Hesse

Mark A Graham

Eddie L Myers

Varinder K Aggarwal

Affiliations

Soon will be listed here.

Abstract

We report the first enantioselective Rh-catalyzed Markovnikov hydroboration of unactivated terminal alkenes. Using a novel sp-sp hybridized diboron reagent and water as a proton source, a broad range of alkenes undergo hydroboration to provide secondary boronic esters with high regio- and enantiocontrol.

Citing Articles

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Desymmetrization of Diboron(4) by a Trifluorination B-Masking Strategy: Practical Synthesis of Unsymmetrical Diboron Species.

Eghbarieh N, Masarwa A J Org Chem. 2024; 89(16):11753-11760.

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Hydroboration of Terminal Alkenes and -1,2-Diboration of Terminal Alkynes Catalyzed by a Manganese(I) Alkyl Complex.

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Zhou J, Meng L, Yang Z, Wang J Adv Sci (Weinh). 2024; 11(21):e2400096.

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Ligand Control in Co-Catalyzed Regio- and Enantioselective Hydroboration: Homoallyl Secondary Boronates via Uncommon 4,3-Hydroboration of 1,3-Dienes.

Parsutkar M, Bhunia S, Majumder M, Lalisse R, Hadad C, RajanBabu T J Am Chem Soc. 2023; 145(13):7462-7481.

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References

Schiffner J, Muther K, Oestreich M . Enantioselective conjugate borylation. Angew Chem Int Ed Engl. 2010; 49(7):1194-6. DOI: 10.1002/anie.200906521. View

Neeve E, Geier S, Mkhalid I, Westcott S, Marder T . Diboron(4) Compounds: From Structural Curiosity to Synthetic Workhorse. Chem Rev. 2016; 116(16):9091-161. DOI: 10.1021/acs.chemrev.6b00193. View

Shoba V, Thacker N, Bochat A, Takacs J . Synthesis of Chiral Tertiary Boronic Esters by Oxime-Directed Catalytic Asymmetric Hydroboration. Angew Chem Int Ed Engl. 2015; 55(4):1465-9. PMC: 4878850. DOI: 10.1002/anie.201509137. View

Toribatake K, Nishiyama H . Asymmetric diboration of terminal alkenes with a rhodium catalyst and subsequent oxidation: enantioselective synthesis of optically active 1,2-diols. Angew Chem Int Ed Engl. 2013; 52(42):11011-5. DOI: 10.1002/anie.201305181. View

Parra A, Amenos L, Guisan-Ceinos M, Lopez A, Garcia Ruano J, Tortosa M . Copper-catalyzed diastereo- and enantioselective desymmetrization of cyclopropenes: synthesis of cyclopropylboronates. J Am Chem Soc. 2014; 136(45):15833-6. DOI: 10.1021/ja510419z. View

Obligacion J, Chirik P . Highly selective bis(imino)pyridine iron-catalyzed alkene hydroboration. Org Lett. 2013; 15(11):2680-3. DOI: 10.1021/ol400990u. View

Sasaki Y, Zhong C, Sawamura M, Ito H . Copper(I)-catalyzed asymmetric monoborylation of 1,3-dienes: synthesis of enantioenriched cyclic homoallyl- and allylboronates. J Am Chem Soc. 2010; 132(4):1226-7. DOI: 10.1021/ja909640b. View

Jang H, Zhugralin A, Lee Y, Hoveyda A . Highly selective methods for synthesis of internal (α-) vinylboronates through efficient NHC-Cu-catalyzed hydroboration of terminal alkynes. Utility in chemical synthesis and mechanistic basis for selectivity. J Am Chem Soc. 2011; 133(20):7859-71. DOI: 10.1021/ja2007643. View

Lee J, Yun J . Catalytic asymmetric boration of acyclic alpha,beta-unsaturated esters and nitriles. Angew Chem Int Ed Engl. 2007; 47(1):145-7. DOI: 10.1002/anie.200703699. View

10.

Noh D, Chea H, Ju J, Yun J . Highly regio- and enantioselective copper-catalyzed hydroboration of styrenes. Angew Chem Int Ed Engl. 2009; 48(33):6062-4. DOI: 10.1002/anie.200902015. View

11.

Coombs J, Morken J . Catalytic Enantioselective Functionalization of Unactivated Terminal Alkenes. Angew Chem Int Ed Engl. 2016; 55(8):2636-49. PMC: 4913282. DOI: 10.1002/anie.201507151. View

12.

Greenhalgh M, Thomas S . Chemo-, regio-, and stereoselective iron-catalysed hydroboration of alkenes and alkynes. Chem Commun (Camb). 2013; 49(95):11230-2. DOI: 10.1039/c3cc46727a. View

13.

Kliman L, Mlynarski S, Morken J . Pt-catalyzed enantioselective diboration of terminal alkenes with B2(pin)2. J Am Chem Soc. 2009; 131(37):13210-1. PMC: 2763309. DOI: 10.1021/ja9047762. View

14.

Rubina M, Rubin M, Gevorgyan V . Catalytic enantioselective hydroboration of cyclopropenes. J Am Chem Soc. 2003; 125(24):7198-9. DOI: 10.1021/ja034210y. View

15.

Lee Y, Hoveyda A . Efficient boron-copper additions to aryl-substituted alkenes promoted by NHC-based catalysts. enantioselective Cu-catalyzed hydroboration reactions. J Am Chem Soc. 2009; 131(9):3160-1. PMC: 2662741. DOI: 10.1021/ja809382c. View

16.

Brown H, Chen G, Jennings M, Ramachandran P . Markovnikov Hydroboration of Perfluoroalkylethylenes. Angew Chem Int Ed Engl. 2021; 38(13-14):2052-2054. DOI: 10.1002/(SICI)1521-3773(19990712)38:13/14<2052::AID-ANIE2052>3.0.CO;2-9. View

17.

Kubota K, Yamamoto E, Ito H . Copper(I)-catalyzed borylative exo-cyclization of alkenyl halides containing unactivated double bond. J Am Chem Soc. 2013; 135(7):2635-40. DOI: 10.1021/ja3104582. View

18.

Guisan-Ceinos M, Parra A, Martin-Heras V, Tortosa M . Enantioselective Synthesis of Cyclobutylboronates via a Copper-Catalyzed Desymmetrization Approach. Angew Chem Int Ed Engl. 2016; 55(24):6969-72. DOI: 10.1002/anie.201601976. View

19.

Thomas S, Aggarwal V . Asymmetric hydroboration of 1,1-disubstituted alkenes. Angew Chem Int Ed Engl. 2009; 48(11):1896-8. DOI: 10.1002/anie.200805604. View

20.

Smith S, Takacs J . Amide-directed catalytic asymmetric hydroboration of trisubstituted alkenes. J Am Chem Soc. 2010; 132(6):1740-1. PMC: 2846594. DOI: 10.1021/ja908257x. View