Ruthenium-Catalyzed Concurrent Tandem Reactions. Greg Boyce University of North Carolina February 8 th 2008
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1 Ruthenium-Catalyzed Concurrent Tandem Reactions Greg Boyce University of North Carolina February 8 th 2008
2 Outline I. Introduction II. Metathesis/Metathesis I. Ring Rearrangement Metathesis II. Enyne Cascades I. Dienyne Metathesis II. Ring Rearrangement Metathesis III. Metathesis/Non-Metathesis I. Metathesis/Isomerization II. Metathesis/Cyclopropanation III. Metathesis/Diels Alder IV. Conclusion
3 Types of Tandem Reactions Tandem reactions are reactions in which multiple bonds are formed in one synthetic operation. Sequential tandem reactions involve coupling transformations that operate independently and often require changes in reaction conditions or the addition of new reagents. Concurrent tandem reactions use a catalyst for multiple cooperative transformations without adding additional reagents or catalysts and the subsequent reactions occur as a consequence of the functionality produced in the previous step. Finnegan, D.; Seigal, B.; Snapper, M. Org. Lett. 2006, 8, Wasilke, J;Obrey, S; Baker, T; Bazan, G. Chem Rev. 2005, 105, 1001.
4 Examples of Sequential and Concurrent Tandem Reactions Sequential Tandem Reaction (Not Covered) Concurrent Tandem Reaction Clark, D. et al. J. Am. Chem. Soc. 2006, 128, Diver, S.; Peppers, B. J. Am. Chem. Soc. 2004, 126, 9524.
5 Disadvantages Atom Economy Efficient Access to Complex Products Potential Side Reactions Catalysts Compatibility Reduces Waste Advantages Eliminates labor and the cost of isolating and purifying intermediates Access to new types of product Higher Yields Wasilke, J;Obrey, S; Baker, T; Bazan, G. Chem Rev. 2005, 105, 1001.
6 Concurrent Tandem vs. Sequential Tandem Reactions Method Yield Concurrent Process 39% Sequential Process Trace Virolleaud, M; Bressy, C; Piva, O. Tetrahedron Lett. 2003, 44, 8081.
7 Benefits in Use of Grubbs Catalysts in Concurrent Tandem Reactions Well-defined, single-site homogenous catalysts Chirality Transfer in metathesis reactions Versatile Metathesis/Isomerization/Hydrogenation/Cyclopropanations High Chemoselectivity (functional group tolerance) in metathesis reactions Trinka, T.; Grubbs, R. Acc. Chem. Res. 2001, 34, 18.
8 Chauvin Mechanism Alkene Complex Metallacyclobutane Leads to a statistic ratio of products in cross metathesis without a driving force J. Hérisson and Y. Chauvin Makromol. Chem. 1971, 141, 161.
9 Outline I. Introduction II. Metathesis/Metathesis I. Ring Rearrangement Metathesis II. Enyne Cascades I. Dienyne Metathesis II. Ring Rearrangement Metathesis III. Metathesis/Non-Metathesis I. Metathesis/Isomerization II. Metathesis/Cyclopropanation III. Metathesis/Diels Alder IV. Conclusion
10 Ring Rearrangement Metathesis Mechanism Ring Rearrangement Metathesis (RRM) - The tandem coupling of ring opening metathesis (ROM) and ring closing metathesis (RCM). Strained cyclic olefins undergo RRM with relief of ring strain as the thermodynamic driving of the reaction Unstrained cyclic olefins undergo RRM with the entropy gain in the formation of the volatile olefin, usually ethylene, as the thermodynamic driving force
11 Ring Rearrangement Metathesis of Cyclic Olefins First published example Zuercher, W. J.; Hashimoto, M.; Grubbs, R. H. J. Am. Chem. Soc. 1996, 118, 6634.
12 Two Possible Mechanisms Zuercher, W. J.; Hashimoto, M.; Grubbs, R. H. J. Am. Chem. Soc. 1996, 118, 6634.
13 Synthesis of α,β-unsaturated Lactones Electron poor olefins usually difficult substrates for metathesis Choi, T; Grubbs, R. Chem. Comm. 2001, 2648.
14 Enantiopure Heterocycle Syntheses Applications to azasugars H. Ovaa et al. Tetrahedron. 2002, 58, Voigtmann, U.; Blechert S. Org. Lett. 2000, 2, 3971.
15 RRM/CM Tandem Sequence and Application to the Total Synthesis of (-)-Lasubine II ROM-RCM-CM Tandem Sequence Applied to (-)-Lasubine II Mirko, Z; Blechert, S. Tetrahedron. 2004, 60, 9629.
16 Regioselectively Restructuring Norbornene Derivatives The products differ in regioselectivity of RCM step. Wrobleski, A.; Sahasrabudhe, K.; Aube, J. J. Am. Chem. Soc. 2004, 126, 5475.
17 Synthesis of the Advanced Intermediate toward Alkaloid 251F RRM Cascade Approach 80% overall yield in 3 steps Alternative Approach (Ozonolysis/Aldol Strategy) 27% overall yield Wrobleski, A.; Sahasrabudhe, K.; Aube, J. J. Am. Chem. Soc. 2004, 126, 5475.
18 Reconstructing Norbornene: Total Synthesis of (+)-Cylindramide A The more active catalyst enables the addition of a CM step Hart, A.; Phillips, A. J. Am. Chem. Soc. 2005, 128, 1094.
19 Outline I. Introduction II. Metathesis/Metathesis I. Ring Rearrangement Metathesis II. Enyne Cascades I. Dienyne Metathesis II. Ring Rearrangement Metathesis III. Metathesis/Non-Metathesis I. Metathesis/Isomerization II. Metathesis/Cyclopropanation III. Metathesis/Diels Alder IV. Conclusion
20 Dienyne Metathesis Mechanism Kim, S.; Bowden, N.; Grubbs, R. J. Am. Chem. Soc. 1994, 116,
21 Dienyne Metathesis of fused bicycles Mono-substitution Directing Effect Kim, S.; Bowden, N.; Grubbs, R. J. Am. Chem. Soc. 1994, 116,
22 Polycyclizations via Enyne/RCM Cascade Zuercher et al. J. Org. Chem. 1998, 63, 4291.
23 Polycyclizations via Enyne/RCM Cascade Zuercher et al. J. Org. Chem. 1998, 63, Nicolaou et al. Angew. Chem. Int. Ed. 2005, 44, 4490.
24 Dienyne Metathesis with Electron Poor Olefins Not observing the 7-membered lactone implies that the terminal alkylidene exclusively reacts with acetylenes over acrylates Choi, T; Grubbs, R. Chem. Comm. 2001, 2648.
25 Formal Synthesis of (+)-Guanacastepene A Boyer et al. Tet. Lett. 2002, 43, Boyer et al. Org. Lett. 2004, 6, 1817.
26 Synthesis of Aza-Cycles via Dienyne Metathesis Tricyclic β-lactams Ynamides to 2-Amidodienes Barrett et al. J. Org. Chem. 1998, 63, Huang et al. Org. Lett. 2002, 4, 2417.
27 Outline I. Introduction II. Metathesis/Metathesis I. Ring Rearrangement Metathesis II. Enyne Cascades I. Dienyne Metathesis II. Ring Rearrangement Metathesis III. Metathesis/Non-Metathesis I. Metathesis/Isomerization II. Metathesis/Cyclopropanation III. Metathesis/Diels Alder IV. Conclusion
28 Enyne Ring Rearrangement Metathesis Kitamura T.; Mori M. Org. Lett. 2001, 3, 1161.
29 Ring Rearrangement of Alkynyl Substituted Cycloolefins: Synthesis of Pyrrolines Kitamura T.; Mori M. Org. Lett. 2001, 3, 1161.
30 Ring Rearrangement Metathesis with Substituted Cyclohexenes Kitamura T.; Mori M. Org. Lett. 2001, 3, 1161.
31 Ring Rearrangement Metathesis with Substituted Cyclohexenes Intramolecular enyne reaction for the cis substrate is inhibited by steric interactions between the [Ru] and the TBDMS group Kitamura T.; Mori M. Org. Lett. 2001, 3, 1161.
32 Ring Rearrangement Metathesis with Substituted Cyclohexenes Intramolecular enyne reaction for the cis substrate is inhibited by steric interactions between the [Ru] and the TBDMS group Kitamura T.; Mori M. Org. Lett. 2001, 3, 1161.
33 Different Grubbs Catalyst, Different Tandem Reaction Synthesis of γ-lactones and Indolizidinones O. Arjona et al. Tet. Lett. 2004, 45, 565.
34 Different Grubbs Catalyst, Different Tandem Reaction Synthesis of γ-lactones and Indolizidinones Product rationale based on catalysts activity O. Arjona et al. Tet. Lett. 2004, 45, 565.
35 Outline I. Introduction II. Metathesis/Metathesis I. Ring Rearrangement Metathesis II. Enyne Cascades I. Dienyne Metathesis II. Ring Rearrangement Metathesis III. Metathesis/Non-Metathesis I. Metathesis/Isomerization II. Metathesis/Cyclopropanation III. Metathesis/Diels Alder IV. Conclusion
36 Ring Closing Metathesis/Olefin Isomerization Cascade Regiochemistry of the Enol Ether Δ Δ Arisawa, M. et al. J. Org. Chem. 2006, 71, Sutton, A; Seigal, B.; Finnegan, D.; Snapper, M. J. Am. Chem. Soc. 2002, 124,
37 Assorted Examples of RCM/Isomerization Cascade Fustero, S. et al. J. Org. Chem. 2005, 71, Arisawa, M. et al. J. Org. Chem. 2006, 71, Schmidt, B.; Biernat, A. Org. Lett. 2008, 10, 105.
38 ROM/CM/Isomerization of Allylic Alcohol Finnegan, D.; Seigal, B.; Snapper, M. Org. Lett. 2006, 8, 2603.
39 Cyclopropanation/RCM of Dienynes Probable Mechanism Diver, S.; Peppers, B. J. Am. Chem. Soc. 2004, 126, 9524.
40 Enyne Metathesis-Cyclopropanation Cascade Cyclopropanation ruthenium catalyst may be different from the metathesis catalyst. 31 P NMR showed new peaks after the tandem reaction Addition of more diene after the tandem reaction does not undergo metathesis Kim B.; Snapper, M. J. Am. Chem. Soc. 2006, 128, 52.
41 Enyne Metathesis-Cyclopropanation Cascade Scope Kim B.; Snapper, M. J. Am. Chem. Soc. 2006, 128, 52.
42 RCM-Isomerization-Cyclopropanation Cascade Kawanaka, Y. et al. Bioorg. Med. Chem , 11, Mallagaray, A.; Dominguez, G.; Gradillas, A.; Pérez-Castells, J. Org. Lett. 2008, ASAP.
43 Synthesis of Fused Tricycles via RRM/CM/Diels Alder Cycloaddition Imhof, S.; Blechert, S. Synlett. 2003, 609.
44 Synthesis of Fused Tricycles via RRM/CM/Diels Alder Cycloaddition Proposed Mechanism Imhof, S.; Blechert, S. Synlett. 2003, 609.
45 Three Component Metathesis/Diels-Alder Cascade Reaction Sequence Lee, H.; Kim, H.; Tae, H.; Kim, B.; Lee, J. Org. Lett. 2003, 5, 3439.
46 Conclusion Ruthenium-catalyzed concurrent tandem reactions enable efficient access to various enantiomerically pure polycycles in a single step The versatility of Grubbs catalysts enable the cooperation of very mechanistically different reactions in effective cascades Although ruthenium-catalyzed concurrent tandem catalysis is still in its infancy its has shown significant
47 Acknowledgements Jeff Johnson Johnson Group
48 Rationale for the Observed Product Wrobleski et al. J. Am. Chem. Soc. 2004, 126, 5475.
49 Ring Rearrangement Mechanism Choi, T; Grubbs, R. Chem. Comm. 2001, 2648.
50 Ruthenium Catalysis: A History 1950 s Discovery of Olefin Metathesis 1970 s - Schrock begins to develop metathesis catalysts using tungsten and molybdenum 197? N. Calderon at Goodyear Tire and Rubber coined the term olefin metathesis 1990 Schrock unveils a very active well-defined catalyst 1992 Grubbs unveils first generation ruthenium catalyst 2005 Grubbs, Shrock and Chauvin awarded the Nobel Prize for their work in metathesis
51 Fused Cyclic Polyethers K.C. Nicolaou et al. Angew. Chem.. Int. Ed. 2001, 40, 4441.
52 Synthesis of Spirocyclic Pyrans from Oxabicyclooctene Derivatives Synthesis of the Oxabicyclooctene derivatives Usher et al. Angew. Chem. Int. Ed. 2002, 41, 4560.
53 Synthesis of Spirocyclic Pyrans- The Importance of Substituent Effects Unsubstituted examples More strained systems Reduced substrates Usher et al. Angew. Chem. Int. Ed. 2002, 114, 4742.
54 Synthesis of Tricyclic Enones from Norbornene Derivatives G1 provides cyclohexa[c]indine skeleton in excellent yield and with high selectivity Holtsclaw J.; Koreeda, M. Org. Lett. 2004, 6, 3719.
55 Synthesis of Tricyclic Enones from Norbornene Derivatives G1 provides cyclohexa[c]indine skeleton in excellent yield and with high selectivity 71% Inseparable by Column Chromatography G1 and G2 gave a poor selectivity for the cyclopenta[c]indine skeleton vs. the undesired tricycle Holtsclaw J.; Koreeda, M. Org. Lett. 2004, 6, 3719.
56 Synthesis of Tricyclic Enones from Norbornene Derivatives G1 provides cyclohexa[c]indine skeleton in excellent yield and with high selectivity 71% Inseparable by Column Chromatography G1 and G2 gave a poor selectivity for the cyclopenta[c]indine skeleton vs. the undesired tricycle G2 provided a very good yield of the allylic alcohol cyclopenta[c]indine Holtsclaw J.; Koreeda, M. Org. Lett. 2004, 6, 3719.
57 Synthesis of Tricyclic Enones from Norbornene Derivatives G1 provides cyclohexa[c]indine skeleton in excellent yield and with high selectivity 71% Inseparable by Column Chromatography G1 and G2 gave a poor selectivity for the cyclopenta[c]indine skeleton vs. the undesired tricycle G2 provided a very good yield of the allylic alcohol cyclopenta[c]indine Holtsclaw J.; Koreeda, M. Org. Lett. 2004, 6, 3719.
58 trans examples Synthesis of Aza-cycles cis examples Slide 13 Five and six membered aza-cycles possible For trans-configured derivatives, yields dramatically improved by switching protecting groups from Ns to benzyloxycarbonyl group R. Stragies and S. Blechert. J. Am. Chem. Soc. 2000, 122, 9584.
59 RRM/CM Cascade of Alkynyl Substituted Cycloolefins Slide 31 and 32 Proposed Mechanism A. Rϋckert et al. Tet. Lett. 2001, 42, 5245.
60 Scope of the RRM/CM for Alkynyl Substituted Cycloolefins A. Rϋckert et al. Tet. Lett. 2001, 42, 5245.
61 Ring Rearrangement Metathesis Mechanism Ring Rearrangement Metathesis (RRM) - The tandem coupling of ring opening metathesis (ROM) and ring closing metathesis (RCM). Strained cyclic olefins undergo RRM with relief of ring strain as the thermodynamic driving of the reaction Unstrained cyclic olefins bearing two olefin substituents can undergo RRM involving a double RCM. The driving force for this reaction is the entropy gain in the formation of the volatile olefin, usually ethylene.
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