Direct and enantioselective a-allylation of ketones via singly occupied molecular orbital (SOMO) catalysis

Proceedings of the National Academy of Sciences of the United States of America

Volumn 107, Issue 48, 2010, Pages 20648-20651

  Mastracchio, Anthony ^a   Warkentin, Alexander A ^a   Walji, Abbas M ^a   MacMillan, David W C ^a  

^a PRINCETON UNIVERSITY   (United States)

Author keywords

Asymmetric synthesis; Organocatalysis

Indexed keywords

KETONE; SILANE DERIVATIVE;

ALLYLATION; CATALYSIS; CHEMICAL STRUCTURE; CONFERENCE PAPER; ENANTIOSELECTIVITY; OXIDATION; PRIORITY JOURNAL; SINGLY OCCUPIED MOLECULAR ORBITAL CATALYSIS;

EID: 78650543169     PISSN: 00278424     EISSN: 10916490     Source Type: Journal    
DOI: 10.1073/pnas.1002845107     Document Type: Article

References (34)

1. Carey FA, Sundberg RJ (2001) Alkylation of nucleophilic carbon intermediates. Advanced Organic Chemistry Part B: Reactions and Synthesis (Kluwer Academic/ Plenum, New York), 4th Ed, pp 1-47.
2. Lu Z, Ma S (2008) Metal-catalyzed enantioselective allylation in asymmetric synthesis. Angew Chem Int Edit 47:258-297.
3. Trost BM, Crawley ML (2003) Asymmetric transition-metal-catalyzed allylic alkylations: Applications in total synthesis. Chem Rev 103:2921-2944.
4. Braun M, Meier T (2006) New developments in stereoselective palladium-catalyzed allylic alkylations of preformed enolates. Synlett 661-676.
5. Doyle AG, Jacobsen EN (2005) Enantioselective alkylations of tributyltin enolates catalyzed by Cr(salen)Cl: Access to enantiomerically enriched all-carbon quaternary centers. J Am Chem Soc 127:62-63.
6. Trost BM, Schroeder GM (1999) Palladium-catalyzed asymmetric alkylation of ketone enolates. J Am Chem Soc 121:6759-6760.
7. Trost BM, Xu J (2005) Regio- and enantioselective Pd-catalyzed allylic alkylation of ketones through allyl enol carbonates. J Am Chem Soc 127:2846-2847.
8. Trost BM, Bream RN, Xu J (2006) Asymmetric allylic alkylation of cyclic vinylogous esters and thioesters by Pd-catalyzed decarboxylation of enol carbonate and β-ketoester substrates. Angew Chem Int Edit 45:3109-3112.
9. Behenna DC, Stoltz BM (2004) The enantioselective Tsuji allylation. J Am Chem Soc 126:15044-15045.
10. Mohr JT, Behenna DC, Harned AM, Stoltz BM (2005) Deracemization of quaternary stereocenters by Pd-catalyzed enantioconvergent decarboxylative allylation of racemic β-ketoesters. Angew Chem Int Edit 44:6924-6927.
11. Braun M, Laicher F, Meier T (2000) Diastereoselective and enantioselective palladiumcatalyzed allylic substitutionwith nonstabilized ketone enolates. Angew Chem Int Edit 39:3494-3497.
12. Braun M, Meier T (2005) Palladium-catalyzed stereoselective allylic alkylation of lithium enolates. Synlett 2968-2972.
13. Graening M, Hartwig JF (2005) Iridium-catalyzed regio- and enantioselective allylation of ketone enolates. J Am Chem Soc 127:17192-17193.
14. Weix DJ, Hartwig JF (2007) Regioselective and enantioselective iridium-catalyzed allylation of enamines. J Am Chem Soc 129:7720-7721.
15. Evans PA, Leahy DK (2003) Regioselective and enantiospecific rhodium-catalyzed allylic alkylation reactions using copper(I) enolates: Synthesis of (-)-sugiresinol dimethyl ether. J Am Chem Soc 125:8974-8975.
16. Yan X-X, et al. (2005) Highly enantioselective Pd-catalyzed allylic alkylations of acyclic ketones. Angew Chem Int Edit 44:6544-6546.
17. Zheng W-H, Zheng B-H, Zhang Y, Hou X-L (2007) Highly regio-, diastereo-, and enantioselective Pd-catalyzed allylic alkylation of acyclic ketone enolates with monosubstituted allyl substrates. J Am Chem Soc 129:7718-7719.
18. Dolling U-H, Davis P, Grabowski EJ (1984) Efficient catalytic asymmetric alkylations. 1. Enantioselective synthesis of (+)-indacrinone via chiral phase-transfer catalysis. J Am Chem Soc 106:446-447.
19. Andrus MB, Hicken EJ, Stephens JC (2004) Phase-transfer-catalyzed asymmetric glycolate alkylation. Org Lett 6:2289-2292.
20. Beeson TD, Mastracchio A, Hong J-B, Ashton K, MacMillan DWC (2007) Enantioselective organocatalysis using SOMO activation. Science 316:582-585.
21. Northrup AB, MacMillan DWC (2002) The first general enantioselective catalytic Diels- Alder reaction with simple a,β-unsaturated ketones. J Am Chem Soc 124:2458-2460.
22. Tuttle JB, Ouellet SG, MacMillan DWC (2006) Organocatalytic transfer hydrogenation of cyclic enones. J Am Chem Soc 128:12662-12663.
23. Lelais G, MacMillan DWC (2006) Modern strategies in organic catalysis: The advent and development of iminium activation. Aldrichim Acta 39:79-87.
24. Mukherjee S, Yang JW, Hoffmann S, List B (2007) Asymmetric enamine catalysis. Chem Rev 107:5471-5569.
25. Conrad JC, Kong J, Laforteza BN, MacMillan DWC (2009) Enantioselective a-arylation of aldehydes via organo-SOMO catalysis. An ortho-selective arylation reaction based on an open-shell pathway. J Am Chem Soc 131:11640-11641.
26. Jang H-Y, Hong J-B, MacMillan DWC (2007) Enantioselective organocatalytic singly occupied molecular orbital activation: The enantioselective a-enolation of aldehydes. J Am Chem Soc 129:7004-7005.
27. Kim H, MacMillan DWC (2008) Enantioselective organo-SOMO catalysis: The a-vinylation of aldehydes. J Am Chem Soc 130:398-399.
28. Graham TH, Jones CM, Jui NT, MacMillan DWC (2008) Enantioselective organo-SOMO catalysis: The carbo-oxidation of styrenes. J Am Chem Soc 130:16494-16495.
29. Wilson JE, Casarez AD, MacMillan DWC (2009) Enantioselective aldehyde a-nitroalkylation via oxidative organocatalysis. J Am Chem Soc 131:11332-11334.
30. Amatore M, Beeson TD, Brown SP, MacMillan DWC (2009) Enantioselective linchpin catalysis by SOMO catalysis: An approach to the asymmetric a-chlorination of aldehydes and terminal epoxide formation. Angew Chem Int Edit 48:5121-5124.
31. Garst ME, Bonfiglio JN, Grudoski DA (1980) Specific enolates from a-amino ketones. J Org Chem 45:2307-2315.
32. Studies are now under way to determine the mechanistic origins of regioselectivity in these allylic alkylations using SOMO activation.
33. Kurth MJ, O'Brien MJ (1986) Desulfurization/a-alkylation of β-keto sulfones. J Org Chem 50:3846-3848.
34. DFT calculations were performed at the B3LYP/6-311+G(2d,p)//B3 LYP/6-31G(d) level of theory using Gaussian 03 software: Frisch MJ, et al. (2004) Gaussian 03 Revision C.02, Gaussian Inc., Wallingford, CT.