Tsuji-Trost reacton

This is a very important reaction as it is regioselective, enantioselectivity and diastereoselectivity  one.

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2. First Pionieered by Prof . Jiro Tsuji in 1965 Later adapted by Prof . Barry M. Trost in 1973 with the introduction of phosphine ligand 2 Discovery First reported reaction Tsuji,J .; Takahasi , H.; Morikawa,M . Tetrahedron Letters, 1965, 6 Trost modified this reaction using the ligand Triphenylphosphine

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5. Trost ligand Chiral ligands 5

6. 6 Chiral ligand

7. The way the reaction takes place differs based on the how hard or soft the incoming nucleophile is… 7 Stereochemistry

8. LG : carbonates , phenols, phosphates, halides, carboxylates Metals : Pd , Mo, Ir Nu : malonates , enolates , primary alkoxides , sulfones , azide , imide C-C, C-N, C-O, C-S bond formation Ambient reaction condition Trost AAA (asymmetric allylic alkylation) H igh r egioselective , enantioselectivity ,  diastereoselectivity   8 Scope

9. 9 Example

10. 10 Example

11. 11 Example

12. 12 Example

13. Tetrahedron . 2015, 71 , 5708-5733. 13 Example

14. 14 Versatility (Not really a bad thing)  Too many parallel reactants  Too many possible reaction conditions  Too many possible outcomes  Some work and some don’t But no need to fear! Tons of Research has been done!!! Limitations

15. RECENT APPLICATIONS 15

16. Synthesis of jiadifenin • Potential for Biological Activity • Parkinson’s and Alzheimer’s Disease • cyclization / lactonization of 15 16 Total Synthesis

17. 17 Palladium Detection

18. Designed 7-nitro-2,1,3-benzoxadiazole-4-allyl-N-( thiophen - 2-ylmethyl) carbamate ( NBDTC) - A New Ratiometric Fluorescent Chemosensor NBDT NBDTC Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy. 2015, 148 , 7-11. 18 Chemosensor

19. References  Tetrahedron Prize 2014 Awarded to Prof. Barry Trost and Jiro Tsuji. https:// www.elsevier.com/physical-sciences/ chemistry/ organicchemistry /tetrahedron-prize-2014-awarded-to-prof .-barry-trost-and-Jiro-Tsuji (accessed Dec 5, 2016).  Tsuji, J.; Takahashi, H.; Morikawa , M. Organic Syntheses By Means Of Noble Metal Compounds XVII. Reaction Of Π- Allylpalladium Chloride With Nucleophiles. Tetrahedron Lett . 1965, 6 , 4387-4388.  Elsevier STM Journals. Interview With Professor Jiro Tsuji - Winnner Of Tetrahedron Prize 2014; 2014.  Tsuji, J. Catalytic Reactions Via π- Allylpalladium Complexes. Pure Appl. Chem. 1982, 54 , 197.  Li, J. Name Reactions: A Collection of Detailed Mechanisms and Synthetic Applications ; 5th ed.; Springer International Publishing Switzerland , 2014; pp. 605-607.  Tsuji- Trost Reaction. http://www.organic-chemistry.org/namedreactions/tsuji-trost-reaction.shtm (accessed Dec 5, 2016).  Trost , B.; Van Vranken , D. Asymmetric Transition Metal- Catalyzed Allylic Alkylations . Chem. Rev. 1996, 96 , 395-422.  Trost , B. Metal Catalyzed Allylic Alkylation: Its Development In The Trost Laboratories. Tetrahedron. 2015, 71 , 5708-5733.  Harada, K.; Imai, A.; Uto , K.; Carter, R.; Kubo, M.; Hioki , H.; Fukuyama, Y. Synthesis Of Jiadifenin Using Mizoroki –Heck And Tsuji– Trost Reactions. Tetrahedron. 2015, 71 , 2199-2209.  Xu , Z.; Li, J.; Guan, S.; Zhang, L.; Dong, C. Highly Selective And Sensitive Fluorescence Chemosensor For The Detection Of Palladium Species Based On Tsuji– Trost Reaction. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy. 2015, 148 , 7-11. 19

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