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(12) Patent Application Publication (10) Pub. No.: US 2006/0084.820 A1 Behenna Et Al US 20060O84820A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2006/0084.820 A1 Behenna et al. (43) Pub. Date: Apr. 20, 2006 (54) ENANTIOSELECTIVE, CATALYTIC Related U.S. Application Data ALLYLATION OF KETONES AND OLEFNS (60) Provisional application No. 60/605.350, filed on Aug. (75) Inventors: Douglas C. Behenna, Elverson, PA 27, 2004. (US); Brian M. Stoltz, Pasadena, CA (US); Justin T. Mohr, Pasadena, CA Publication Classification (US); Andrew M. Harned, Pasadena, CA (US) (51) Int. C. C07F 7/08 (2006.01) Correspondence Address: CD7C 69/66 (2006.01) REED INTELLECTUAL PROPERTY LAW (52) U.S. Cl. ............................................ 556/437; 560/174 GROUP (57) ABSTRACT 1400 PAGE MILL ROAD Compounds containing a Substituted or unsubstituted allyl PALO ALTO, CA 94304-1124 (US) group directly bound to a chiral carbon atom are prepared (73) Assignee: California Institute of Technology, enantioselectively. Starting reactants are either chiral or achiral, and may or may not contain an attached allyloxy Pasadena, CA (US) carbonyl group as a Substituent. Chiral ligands are (21) Appl. No.: 11/215,449 employed, along with transition metal catalysts. The meth ods of the invention are effective in providing enantiocon (22) Filed: Aug. 29, 2005 vergent allylation of chiral molecules. US 2006/0084.820 A1 Apr. 20, 2006 ENANTIOSELECTIVE, CATALYTICALLYLATION 3-diketones and 3-ketoesters using prochiral electrophiles, OF KETONES AND OLEFNS or to C-aryl ketones and cyclic ketones that can only form a single enolate (Hayashi et al. (1988) J. Org. Chem. 53: CROSS REFERENCE TO RELATED 113-120: Sawamura et al., (1992) J. Am. Chem. Soc. 114: APPLICATION 2586-2592: Trost et al. (1997) J. Am. Chem. Soc. 119: 7879-7880; Kuwano, et al. (1999) J. Am. Chem. Soc. 121: 0001. This application claims priority under 35 U.S.C. S 3236-3237; Trost et al. (1999) J. Am. Chem. Soc. 121: 119(e)(1) to Provisional U.S. Patent Application Ser. No. 6759-6760; You et al. (2001) Org. Lett. 3:149-151; Trost et 60/605.350, filed Aug. 27, 2004, the disclosure of which is al. (2002) Angew. Chem. Int. Ed. 41: 3492-3495). In general, incorporated herein by reference in its entirety. strongly basic conditions are required in order to form the reactive enolate intermediate. For example, Trost et al. TECHNICAL FIELD (2002) describes the allylation of C-aryl ketones using the strongly basic reagents lithium diisoproplyamide or sodium 0002 The present invention relates in general to enanti 1,1,1,3,3,3-hexamethyldisilazide. Hayashi et al. described oselective allylation reactions. In particular, the invention the enantioselective allylation of B-diketones using a palla relates to enantioselective carbon-carbon bond formation dium catalyst, while Trost et al. (1997) has shown similar reactions, and the methods of the invention are useful in results for B-ketoester Substrates. Sugimoto et al. used synthetic organic chemistry. chromium(III) complexes in order to catalyze enantioselec tive allylation reactions of aldehydes. Titanium(IV) catalysts BACKGROUND were used by Satoshi et al. in order to enantioselectively 0003 Allylic alkylations form an important class of reac allylate certain ketones. tions in synthetic organic chemistry (Trost et al. (2002) 0007. In light of the limited success in developing enan Chem. Pharm. Bull. (Tokyo) 50:1-14; Hayashi et al. (1988) tioselective allylation reactions, there exists a need in the art J. Org. Chem. 53: 113-120: Trost et al. (1997).J. Am. Chem. for a method to prepare highly enantioenriched C-quaternary Soc. 119: 7879-7880; Sugimoto et al. (1997).J. Org. Chem. cycloalkanones and related compounds via enantioselective 62: 2322-2323; Satoshi et al. (2003) Chirality 15: 68-70). allylation. Such a method would, optimally, tolerate of a The unique reactivity of compounds containing allylic wide variety of functional groups on the Substrate, require groups accounts for their utility in synthetic transformations mild reaction conditions, and employ readily available cata and multi-step syntheses. Although numerous methods exist lyst/ligand systems. Also desirable is the ability to carry out for adding allyl groups onto compounds displaying a variety the reaction on a broad range of structurally distinct com of structures and functional groups, current limitations have pounds. Flexibility in the choice of the catalyst system is generated much effort towards expanding the scope of the also highly desirable. transformation. 0004. A well-established approach towards allylic alky BRIEF DESCRIPTION OF THE INVENTION lation is via simple nucleophilic substitution. Under basic conditions, alcohols, amines and carbanion precursors such 0008. In one embodiment of the invention, a method is as malonates form nucleophiles that react with alkyl halides provided for synthesizing a compound containing a Substi or triflates to form the corresponding O N— or C-alky tuted or unsubstituted allyl group directly bound to a chiral lated products. As an example of this method, allylic alky carbon atom. The method comprises contacting an allyloxy lation of these nucleophilic Substrates can be achieved using carbonyl-substituted reactant with a transition metal catalyst allyl halides. Regio- and stereocontrol over the alkylation in the presence of a chiral ligand. The allyloxycarbonyl product, however, is highly dependent upon the structure of group can be optionally Substituted with one or more non the reactant. hydrogen Substituents. 0005. An important subset of allylation reactions in gen 0009. In a further embodiment of the invention, a method eral is the formation of C-allyl ketones. Allylation of allyl is provided for enantioselectively allylating an olefinic sub enol carbonates is one approach toward this goal. As origi strate. The method comprises contacting the Substrate with nally described (Tsuji et al. (1987) Acc. Chem. Res. 20: an allylating reagent in the presence of a transition metal 140-145: Tsuji et al. (1983) Tetrahedron Lett. 24; 1793 catalyst and a chiral ligand under reaction conditions effec 1796: Tsuji et al. (1985).J. Org. Chem. 50: 1523-1529; Tsuji tive to provide a compound containing a substituted or et al. (1983) Chem. Lett. 12: 1325-1326), a palladium unsubstituted allyl group. The substituted or unsubstituted catalyst is used in conjunction with a phosphine ligand Such allyl group is directly bound to a chiral carbon atom. The as PPh. The reaction proceeds via decarboxylative degra olefinic substrate has the structure of formula (I) dation of the starting material to form, in situ, an electro philic allyl moiety and a nucleophilic enolate. The reaction affords excellent regiocontrol, and occurs under essentially (I) neutral conditions. Unfortunately, the allylation reported by Tsuji et al. displays no stereocontrol; the reaction results in a racemic mixture of C-allylcyclohexanone products. As a result of the lack of stereocontrol, this approach has since been used and reported as a synthetic tool only sparingly. 0006 Synthetic methods for preparing C-quaternary car bons are generally more useful when the products are wherein, in formula (I): enantioenriched. Enantioselectivity has been achieved in allylation reactions for a limited pool of Substrates using a 0010) R', R, and R are independently selected from H, Palladium catalyst in conjunction with chiral ligands. These hydrocarbyl, substituted hydrocarbyl, heteroatom-contain systems have been essentially confined to allylation of ing hydrocarbyl, Substituted heteroatom-containing hydro US 2006/0084.820 A1 Apr. 20, 2006 carbyl, and functional groups, wherein any two of R', R, atoms, such as methyl, ethyl, n-propyl, isopropyl. n-butyl, and R may be taken together to form a cycle; isobutyl, t-butyl, octyl, decyl, and the like, as well as 0011 Y is selected from —OR. - NRR, and SR", in cycloalkyl groups such as cyclopentyl, cyclohexyl and the which: like. Generally, although again not necessarily, alkyl groups herein contain 1 to about 12 carbon atoms. The term “lower 0012 R is selected from SiRRR', SnRRR', and alkyl intends an alkyl group of 1 to 6 carbon atoms, BR'R'', wherein R. R. and R'' are independently preferably 1 to 4 carbon atoms, and the specific term selected from hydrocarbyl and substituted hydrocarbyl, R' “cycloalkyl intends a cyclic alkyl group, typically having 4 and R'' are independently selected from hydrocarbyl, sub to 8, preferably 5 to 7, carbon atoms. The term “substituted stituted hydrocarbyl, heteroatom-containing hydrocarbyl, alkyl refers to alkyl substituted with one or more substitu and Substituted heteroatom-containing hydrocarbyl, and can ent groups, and the terms "heteroatom-containing alkyl and optionally be taken together to form a cycle; "heteroalkyl refer to alkyl in which at least one carbonatom 0013 Rand Rare independently selected from Mg, Li, is replaced with a heteroatom. If not otherwise indicated, the Zn, hydrocarbyl, substituted hydrocarbyl, heteroatom-con terms “alkyl and “lower alkyl include linear, branched, taining hydrocarbyl, and Substituted heteroatom-containing cyclic, unsubstituted, Substituted, and/or heteroatom-con hydrocarbyl, and Rand R' can optionally be taken together taining alkyl and lower alkyl, respectively. to form a cycle; and 0022. The term “alkenyl as used herein refers to a linear, 0014) R' is hydrogen or hydrocarbyl. branched or cyclic hydrocarbon group of 2 to 24 carbon atoms containing at least one double bond. Such as ethenyl, 0015. In a further embodiment of the reaction, a method n-propenyl,
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