Relative Reactivity of Alkenyl Alcohols in the Palladium-catalyzed Redox-relay Heck Reaction

Overview

Journal Tetrahedron

Specialty Chemistry

Date 2015 Sep 23

PMID 26392640

Citations 11

Authors

Margaret J Hilton

Bin Cheng

Benjamin R Buckley

Liping Xu

Olaf Wiest

Matthew S Sigman

Affiliations

Soon will be listed here.

Abstract

The relative rates of alkenyl alcohols in the Pd-catalyzed redox-relay Heck reaction were measured in order to examine the effect of their steric and electronic properties on the rate-determining step. Competition experiments between an allylic alkenyl alcohol and two substrates with differing chain lengths revealed that the allylic alcohol reacts 3-4 times faster in either case. Competition between di- and trisubstituted alkenyl alcohols provided an interesting scenario, in which the disubstituted alkene was consumed first followed by reaction of the trisubstituted alkene. Consistent with this observation, the transition structures for the migratory insertion of the aryl group into the di- and trisubstituted alkenes were calculated with a lower barrier for the former. An internal competition between a substrate containing two alcohols with differing chain lengths demonstrated the catalyst's preference for migrating towards the closest alcohol. Additionally, it was observed that increasing the electron density in the arene boronic acid promotes a faster reaction, which correlates with Hammett σ values to give a ρ of -0.87.

Citing Articles

Stereoselective Synthesis of 1,n-Dicarbonyl Compounds Through Palladium-Catalyzed Ring Opening/Isomerization of Densely Substituted Cyclopropanols.

Teschers C, Cohen A, Marek I Angew Chem Int Ed Engl. 2024; 64(6):e202421476.

PMID: 39563646 PMC: 11795715. DOI: 10.1002/anie.202421476.

Mechanistic Insights on the Selectivity of the Tandem Heck-Ring-Opening of Cyclopropyldiol Derivatives.

Cohen A, Kaushansky A, Marek I JACS Au. 2022; 2(3):687-696.

PMID: 35373195 PMC: 8970019. DOI: 10.1021/jacsau.1c00547.

Ru-catalyzed isomerization of ω-alkenylboronates towards stereoselective synthesis of vinylboronates with subsequent functionalization.

Ho G, Segura L, Marek I Chem Sci. 2021; 11(23):5944-5949.

PMID: 34094086 PMC: 8159340. DOI: 10.1039/d0sc02542a.

Rate Profiling the Impact of Remote Functional Groups on the Redox-Relay Heck Reaction.

Kraus S, Ross S, Sigman M Org Lett. 2021; 23(7):2505-2509.

PMID: 33710906 PMC: 8026703. DOI: 10.1021/acs.orglett.1c00450.

Enantioselective Synthesis of γ-Functionalized Cyclopentenones and δ-Functionalized Cycloheptenones Utilizing a Redox-Relay Heck Strategy.

Yuan Q, Prater M, Sigman M Adv Synth Catal. 2021; 362(2):326-330.

PMID: 33447174 PMC: 7806184. DOI: 10.1002/adsc.201901239.

References

Yoo K, Park C, Yoon C, Sakaguchi S, ONeill J, Jung K . Asymmetric intermolecular heck-type reaction of acyclic alkenes via oxidative palladium(II) catalysis. Org Lett. 2007; 9(20):3933-5. DOI: 10.1021/ol701584f. View

Yoo K, ONeill J, Sakaguchi S, Giles R, Lee J, Jung K . Asymmetric intermolecular boron Heck-type reactions via oxidative palladium(II) catalysis with chiral tridentate NHC-amidate-alkoxide ligands. J Org Chem. 2009; 75(1):95-101. PMC: 2798920. DOI: 10.1021/jo901977n. View

Patel H, Sigman M . Palladium-catalyzed enantioselective Heck alkenylation of acyclic alkenols using a redox-relay strategy. J Am Chem Soc. 2015; 137(10):3462-5. PMC: 4785804. DOI: 10.1021/ja5130836. View

Mc Cartney D, Guiry P . The asymmetric Heck and related reactions. Chem Soc Rev. 2011; 40(10):5122-50. DOI: 10.1039/c1cs15101k. View

Dounay A, Overman L . The asymmetric intramolecular Heck reaction in natural product total synthesis. Chem Rev. 2003; 103(8):2945-64. DOI: 10.1021/cr020039h. View

Xu L, Hilton M, Zhang X, Norrby P, Wu Y, Sigman M . Mechanism, reactivity, and selectivity in palladium-catalyzed redox-relay Heck arylations of alkenyl alcohols. J Am Chem Soc. 2014; 136(5):1960-7. PMC: 3985895. DOI: 10.1021/ja4109616. View

Burns N, Baran P, Hoffmann R . Redox economy in organic synthesis. Angew Chem Int Ed Engl. 2009; 48(16):2854-67. DOI: 10.1002/anie.200806086. View

Crawley M, Phipps K, Goljer I, Mehlmann J, Lundquist J, Ullrich J . Efficient, regioselective palladium-catalyzed tandem Heck-isomerization reaction of aryl bromides and non-allylic benzyl alcohols. Org Lett. 2009; 11(5):1183-5. DOI: 10.1021/ol900036y. View

Dang Y, Qu S, Wang Z, Wang X . A computational mechanistic study of an unprecedented Heck-type relay reaction: insight into the origins of regio- and enantioselectivities. J Am Chem Soc. 2014; 136(3):986-98. DOI: 10.1021/ja410118m. View

10.

Woodmansee D, Pfaltz A . Asymmetric hydrogenation of alkenes lacking coordinating groups. Chem Commun (Camb). 2011; 47(28):7912-6. DOI: 10.1039/c1cc11430a. View

11.

Consorti C, Flores F, Dupont J . Kinetics and mechanistic aspects of the Heck reaction promoted by a CN-palladacycle. J Am Chem Soc. 2005; 127(34):12054-65. DOI: 10.1021/ja051834q. View

12.

Mei T, Werner E, Burckle A, Sigman M . Enantioselective redox-relay oxidative heck arylations of acyclic alkenyl alcohols using boronic acids. J Am Chem Soc. 2013; 135(18):6830-3. PMC: 3698857. DOI: 10.1021/ja402916z. View

13.

Hilton M, Xu L, Norrby P, Wu Y, Wiest O, Sigman M . Investigating the nature of palladium chain-walking in the enantioselective redox-relay Heck reaction of alkenyl alcohols. J Org Chem. 2014; 79(24):11841-50. PMC: 4275159. DOI: 10.1021/jo501813d. View

14.

Mei T, Patel H, Sigman M . Enantioselective construction of remote quaternary stereocentres. Nature. 2014; 508(7496):340-4. PMC: 4007023. DOI: 10.1038/nature13231. View

15.

Milo A, Bess E, Sigman M . Interrogating selectivity in catalysis using molecular vibrations. Nature. 2014; 507(7491):210-4. DOI: 10.1038/nature13019. View

16.

Werner E, Mei T, Burckle A, Sigman M . Enantioselective Heck arylations of acyclic alkenyl alcohols using a redox-relay strategy. Science. 2012; 338(6113):1455-8. PMC: 3583361. DOI: 10.1126/science.1229208. View

17.

Renata H, Zhou Q, Baran P . Strategic redox relay enables a scalable synthesis of ouabagenin, a bioactive cardenolide. Science. 2013; 339(6115):59-63. PMC: 4365795. DOI: 10.1126/science.1230631. View

18.

Oliveira C, Angnes R, Correia C . Intermolecular enantioselective Heck-Matsuda arylations of acyclic olefins: application to the synthesis of β-aryl-γ-lactones and β-aryl aldehydes. J Org Chem. 2013; 78(9):4373-85. DOI: 10.1021/jo400378g. View

19.

Weinstein A, Schuman D, Tan Z, Stahl S . Synthesis of vicinal aminoalcohols by stereoselective aza-Wacker cyclizations: access to (-)-acosamine by redox relay. Angew Chem Int Ed Engl. 2013; 52(45):11867-70. PMC: 3943752. DOI: 10.1002/anie.201305926. View

20.

Angnes R, Oliveira J, Oliveira C, Martins N, Correia C . Stereoselective synthesis of aryl cyclopentene scaffolds by Heck-Matsuda desymmetrization of 3-cyclopentenol. Chemistry. 2014; 20(41):13117-21. DOI: 10.1002/chem.201404159. View