A Three-Component Coupling Strategy for Tetrahydrofuran Synthesis: Application of the Diisopropyl Tartrate Modified (E)-γ-(Dimethylphenylsilyl)allylboronate as an α,γ-Allyl Dianion Equivalent

A highly convergent three-component coupling strategy for the stereocontrolled synthesis of 2,3,5-trisubstituted tetrahydrofurans is described. After allylboration of the first aldehyde with 1, the chiral, nonracemic allylsilanes 2 are coupled with a second aldehyde or ketone with Lewis acid catalysis to give tetrahydrofurans 3 or 4 with excellent selectivity. The 2,5-stereochemistry is controlled by operating under nonchelate (e.g., 3) or chelate (e.g., 4) conditions.

[1]  K. Woerpel,et al.  The [3 + 2] Annulation of Allylsilanes and Chlorosulfonyl Isocyanate: Stereoselective Synthesis of 2-Pyrrolidinones. , 1999, The Journal of organic chemistry.

[2]  K. Woerpel,et al.  Copper-Mediated Substitution Reactions of Alkylmagnesium Reagents with Allylic Carbamates: (Z)-Selective Alkene Synthesis , 1998 .

[3]  Ping Liu,et al.  Studies directed toward the total synthesis of kabiramide C: Asymmetric synthesis of the C7–C19 fragment , 1998 .

[4]  W. Roush,et al.  4,5-Diisopropyl-B-[(E)-[(3‘-menthofuryl)dimethylsilyl]allyl]-1,3,2- dioxaborolane, an Improved Chiral Reagent for the Anti α-Hydroxyallylation of Aldehydes: Application to the Enantioselective Synthesis of (−)-Swainsonine , 1997 .

[5]  Y. Landais,et al.  The oxidation of the carbon-silicon bond , 1996 .

[6]  A. Matsumoto,et al.  New Synthesis of (E)-Allylsilanes with High Enantiopurity via Diastereoselective Intramolecular Bis-Silylation of Chiral Allylic Alcohols , 1996 .

[7]  C. Masse,et al.  Diastereoselective Reactions of Chiral Allyl and Allenyl Silanes with Activated C:X .pi.-Bonds , 1995 .

[8]  K. Savin,et al.  Effects of olefin geometry on the stereochemistry of Lewis acid mediated additions of crotylstannanes to aldehydes , 1994 .

[9]  S. Denmark,et al.  Stereochemical studies on the addition of allylstannanes to aldehydes. The SE' component , 1994 .

[10]  K. Ishikawa,et al.  Stereoselective Construction of Tetrahydrofuran by Tin (IV) Chloride Promoted [3+2] Cycloaddition of Allylsilane to α-Keto Ester , 1994 .

[11]  J. Panek,et al.  Double stereodifferentiation in the Lewis acid promoted addition of chiral (E)-crotylsilanes with (S)-2-(benzyloxy)propanal. Effect of Lewis acid on reaction diastereoselection , 1993 .

[12]  P. Cirillo,et al.  Acyclic diastereoselectivity in the Lewis acid promoted additions of chiral, .beta.-methyl-substituted (E)-crotylsilanes with achiral aldehydes , 1993 .

[13]  W. Roush,et al.  Diisopropyl tartrate modified (E)-γ-[(cyclohexyloxy)dimethylsilyl]- and (E)-γ-(dimethylphenylsilyl)allylboronates: Chiral Reagents for the Enantio- and Diastereoselective synthesis of anti 1,2-diols and 2-butene-1,4-diols via the formal α- and γ-hydroxyallylation of aldehydes , 1992 .

[14]  Michael G. Yang,et al.  Diastereoselective additions of chiral (E)-crotylsilanes to .alpha.-alkoxy and .beta.-alkoxy aldehydes. A one-step, silicon-directed tetrahydrofuran synthesis , 1991 .

[15]  T. Nakai,et al.  Anomalous threo-diastereoselectivity in allylic silane- or stannane–aldehyde condensation reactions: new interpretation of the antiperiplanar vs. synclinal problem on the transition-state conformations , 1990 .

[16]  T. Willson,et al.  Stereochemical and spectroscopic studies on the reaction of allylstannanes with aldehydes , 1989 .

[17]  P. F. Hudrlik,et al.  Protiodesilylation reactions of β- and γ-hydroxysilanes: Deuterium labeling and silicon-directed epoxide openings , 1988 .

[18]  H. Brown,et al.  Chiral synthesis via organoboranes. 7. Diastereoselective and enantioselective synthesis of erythro- and threo-.beta.-methylhomoallyl alcohols via enantiomeric (Z)- and (E)-crotylboranes. , 1986, Journal of the American Chemical Society.

[19]  R. Danheiser,et al.  Application of allenylsilanes in [3+2] annulation approaches to oxygen and nitrogen heterocycles , 1985 .

[20]  D. Potenza,et al.  Stereoselective aldol reactions using ticl4 as stereochemical template , 1985 .

[21]  P. F. Hudrlik,et al.  Protodesilylation reactions of simple .beta.-hydroxysilanes (and .alpha.-hydroxysilanes). Homo-Brook rearrangements , 1982 .