Chiral Cyclopentadienylruthenium Sulfoxide Catalysts for Asymmetric Redox Bicycloisomerization

Overview

Journal Beilstein J Org Chem

Specialty Chemistry

Date 2016 Aug 26

PMID 27559366

Citations 1

Authors

Barry M Trost

Michael C Ryan

Meera Rao

Affiliations

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Abstract

A full account of our efforts toward an asymmetric redox bicycloisomerization reaction is presented in this article. Cyclopentadienylruthenium (CpRu) complexes containing tethered chiral sulfoxides were synthesized via an oxidative [3 + 2] cycloaddition reaction between an alkyne and an allylruthenium complex. Sulfoxide complex 1 containing a p-anisole moiety on its sulfoxide proved to be the most efficient and selective catalyst for the asymmetric redox bicycloisomerization of 1,6- and 1,7-enynes. This complex was used to synthesize a broad array of [3.1.0] and [4.1.0] bicycles. Sulfonamide- and phosphoramidate-containing products could be deprotected under reducing conditions. Catalysis performed with enantiomerically enriched propargyl alcohols revealed a matched/mismatched effect that was strongly dependent on the nature of the solvent.

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References

Trost B, Ryan M, Rao M, Markovic T . Construction of enantioenriched [3.1.0] bicycles via a ruthenium-catalyzed asymmetric redox bicycloisomerization reaction. J Am Chem Soc. 2014; 136(50):17422-5. DOI: 10.1021/ja510968h. View

Wender P, Verma V, Paxton T, Pillow T . Function-oriented synthesis, step economy, and drug design. Acc Chem Res. 2007; 41(1):40-9. DOI: 10.1021/ar700155p. View

Watson I, Ritter S, Toste F . Asymmetric synthesis of medium-sized rings by intramolecular Au(I)-catalyzed cyclopropanation. J Am Chem Soc. 2009; 131(6):2056-7. PMC: 2662771. DOI: 10.1021/ja8085005. View

Laurent B, Grayson S . Synthetic approaches for the preparation of cyclic polymers. Chem Soc Rev. 2009; 38(8):2202-13. DOI: 10.1039/b809916m. View

Martinez A, Garcia-Garcia P, Fernandez-Rodriguez M, Rodriguez F, Sanz R . Gold(I)-catalyzed enantioselective synthesis of functionalized indenes. Angew Chem Int Ed Engl. 2010; 49(27):4633-7. DOI: 10.1002/anie.201001089. View

Teller H, Furstner A . Concise synthesis of the antidepressive drug candidate GSK1360707 by a highly enantioselective gold-catalyzed enyne cycloisomerization reaction. Chemistry. 2011; 17(28):7764-7. DOI: 10.1002/chem.201101346. View

Chao C, Vitale M, Toullec P, Genet J, Michelet V . Asymmetric gold-catalyzed hydroarylation/cyclization reactions. Chemistry. 2009; 15(6):1319-23. DOI: 10.1002/chem.200802341. View

Kanbayashi N, Takenaka K, Okamura T, Onitsuka K . Asymmetric auto-tandem catalysis with a planar-chiral ruthenium complex: sequential allylic amidation and atom-transfer radical cyclization. Angew Chem Int Ed Engl. 2013; 52(18):4897-901. DOI: 10.1002/anie.201300485. View

Nicolaou , Vourloumis , Winssinger , Baran . The Art and Science of Total Synthesis at the Dawn of the Twenty-First Century. Angew Chem Int Ed Engl. 2000; 39(1):44-122. View

10.

Zhang Q, Lu X, Han X . Palladium(II)-catalyzed asymmetric cyclization of (Z)-4'-acetoxy-2'-butenyl 2-alkynoates. Role of nitrogen-containing ligands in palladium(II)-mediated reactions. J Org Chem. 2001; 66(23):7676-84. DOI: 10.1021/jo0105181. View

11.

Hatano M, Terada M, Mikami K . Highly Enantioselective Palladium-Catalyzed Ene-Type Cyclization of a 1,6-Enyne We are grateful to Drs. H. Kumobayashi, T. Miura, and N. Sayo of Takasago International Co. for providing the BINAP and SEGPHOS ligands. We also thank Dr. M. Yamasaki.... Angew Chem Int Ed Engl. 2001; 40(1):249-253. View

12.

Onitsuka K, Okuda H, Sasai H . Regio- and enantioselective o-allylation of phenol and alcohol catalyzed by a planar-chiral cyclopentadienyl ruthenium complex. Angew Chem Int Ed Engl. 2008; 47(8):1454-7. DOI: 10.1002/anie.200704457. View

13.

Michelet V, Toullec P, Genet J . Cycloisomerization of 1,n-enynes: challenging metal-catalyzed rearrangements and mechanistic insights. Angew Chem Int Ed Engl. 2008; 47(23):4268-315. DOI: 10.1002/anie.200701589. View

14.

Trost B . The atom economy--a search for synthetic efficiency. Science. 1991; 254(5037):1471-7. DOI: 10.1126/science.1962206. View

15.

Nishimura T, Maeda Y, Hayashi T . Chiral diene-phosphine tridentate ligands for rhodium-catalyzed asymmetric cycloisomerization of 1,6-enynes. Org Lett. 2011; 13(14):3674-7. DOI: 10.1021/ol2013236. View

16.

Kanbayashi N, Onitsuka K . Ruthenium-catalyzed regio- and enantioselective allylic substitution with water: direct synthesis of chiral allylic alcohols. Angew Chem Int Ed Engl. 2011; 50(22):5197-9. DOI: 10.1002/anie.201101078. View

17.

Maas G . Ruthenium-catalysed carbenoid cyclopropanation reactions with diazo compounds. Chem Soc Rev. 2004; 33(3):183-90. DOI: 10.1039/b309046a. View

18.

Trost B, Rao M, Dieskau A . A chiral sulfoxide-ligated ruthenium complex for asymmetric catalysis: enantio- and regioselective allylic substitution. J Am Chem Soc. 2013; 135(49):18697-704. DOI: 10.1021/ja411310w. View

19.

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

20.

Shintani R, Nakatsu H, Takatsu K, Hayashi T . Rhodium-catalyzed asymmetric [5+2] cycloaddition of alkyne-vinylcyclopropanes. Chemistry. 2009; 15(35):8692-4. DOI: 10.1002/chem.200901463. View