A new protocol for the acetoxyallylation of aldehydes mediated by indium in THF.

A new precursor of a formal 1-hydroxy allyl anion is represented by 3-bromo-1-acetoxy-1-propene, which is synthesized by the ZnCl(2)-catalyzed addition of acetyl bromide to propenal. 3-Bromo-1-acetoxy-1-propene reacts with indium powder in THF to give the corresponding 3-acetoxylated ally indium complex, which regioselectively adds to aldehydes, affording monoprotected 1-en-3,4-diols. Diastereoselectivity mainly depends on the nature of the aldehyde; saturated aldehydes afford anti adducts, whereas the alpha,beta-unsaturated aldehydes preferentially lead to the syn isomers. Reaction: see text.

[1]  W. Roush,et al.  Studies on the synthesis of pectenotoxin II: synthesis of a C(11)-C(26) fragment precursor via [3 + 2]-annulation reactions of chiral allylsilanes. , 2001, Organic letters.

[2]  W. Roush,et al.  Synthesis of the C(29)-C(45) bis-pyran subunit (E-F) of spongistatin 1 (Altohyrtin A). , 2000, The Journal of organic chemistry.

[3]  Nadège Lubin-Germain,et al.  Indium-catalyzed allylation of carbonyl compounds with the Mn/TMSCl system , 1999 .

[4]  Chao-Jun Li,et al.  Organic syntheses using indium-mediated and catalyzed reactions in aqueous media , 1999 .

[5]  W. Roush,et al.  Towards the synthesis of spongistatin 1: Diastereoselective synthesis of the C(36)–C(45) subunit , 1999 .

[6]  A. Katritzky,et al.  Regioselectivity of the Reactions of Heteroatom-Stabilized Allyl Anions with Electrophiles. , 1999, Chemical reviews.

[7]  T. Horie,et al.  Preparation of gamma-Heterosubstituted Allylindium and Diindium Reagents and Their Reactions with Carbonyl Compounds. , 1999, The Journal of organic chemistry.

[8]  M. Lombardo,et al.  A Route to (2α,3β,4α)-(±)-2-(Hydroxymethyl)-3,4-pyrrolidinediol Based on the α-Silyloxyallylation of a Glycolaldehyde-Derived Nitrone , 1998 .

[9]  H. Takei,et al.  Arabinose as a chiral auxiliary for the asymmetric α-hydroxyallylation of aldehydes to syn-1,2-diols , 1998 .

[10]  J. Parrain,et al.  Addition of α-Substituted (γ-Alkoxyallyl)tins on Aldehydes: The Dramatic Influence of the Size of the α-Substituent on the Diastereoselection , 1997 .

[11]  L. Paquette,et al.  Experimental Test of Setting Three Contiguous Stereogenic Centers in Water. Diastereoselective Coupling of Geometrically Biased Allylic Bromides to α-Oxy Aldehydes with Indium , 1997 .

[12]  K. Nicholas,et al.  Reactions of Cobalt-Complexed Acetylenic Aldehydes with Chiral (γ-Alkoxyallyl)boranes: Enantioselective Synthesis of 3,4-Dioxy 1,5-Enynes and Stereoselective Entry to Polyfunctional Building Blocks , 1997 .

[13]  Chao‐Jun Li.  Aqueous Barbier-Grignard Type Reaction: Scope, Mechanism, and Synthetic Applications , 1996 .

[14]  P. Cintas.  Synthetic Organoindium Chemistry: What Makes Indium so Appealing? , 1995 .

[15]  Songchun Jiang,et al.  BF3.cntdot.Et2O-Promoted Allylation Reactions of Allyl(cyclopentadienyl)iron(II) Dicarbonyl Complexes with Carbonyl Compounds , 1995 .

[16]  H. Brown,et al.  [(E)-.gamma.-(1,3,2-Dioxaborinanyl)allyl]diisopinocampheylborane, an Exceptional Reagent for the Stereo- and Enantioselective Synthesis of anti- 1-Alkene-3,4-diols via a Masked .alpha.-Hydroxyallylboration , 1995 .

[17]  K. Hinkle,et al.  Synthesis of anti-Homoallylic Alcohols and Monoprotected 1,2-Diols through InCl3-Promoted Addition of Allylic Stannanes to Aldehydes , 1995 .

[18]  W. Roush,et al.  Diisopropyl tartrate-modified (E)-γ-[(menthofuryl)dimethylsilyl]-allyl boronate, an improved chiral reagent for the anti α-hydroxyallylation of aldehydes. Application to the enantioselective synthesis of (−)-swainsonine , 1995 .

[19]  M. VanNieuwenhze,et al.  [(Z)-.gamma.-[(Diisopropylidene-.alpha.-D-mannopyranosyl)oxy]allyl]tributylstannane: A New Chiral Reagent for the Asymmetric .alpha.-Hydroxyallylation of Aldehydes , 1994 .

[20]  W. Roush,et al.  Diisopropyl tartrate modified (E)-γ-[(cyclohexyloxy)dimethylsilyl-allylboronate, a chiral reagent for the stereoselective synthesis of anti 1,2-diols via the formal α-hydroxyallylation of aldehydes , 1990 .

[21]  K. Takai,et al.  Reduction of acrolein dialkyl, acetals with CrCl2. γy-alkoxy substitued allylic chromium reagents for selective synthesis of erythro-1, 2-diols. , 1988 .

[22]  R. W. Hoffmann,et al.  Stereoselective Syntheses of Alcohols, XXIV. Synthesis of 2,6‐Dideoxy‐L‐hexoses , 1987 .

[23]  K. Tamao,et al.  Silafunctional compounds in organic synthesis. 33. Metalated allylaminosilane: a new, practical reagent for the stereoselective .alpha.-hydroxyallylation of aldehydes to erythro-1,2-diol skeletons , 1987 .

[24]  G. E. Keck,et al.  New allylstannanes for the connective construction of monoprotected vicinal diols , 1987 .

[25]  K. Maruyama,et al.  Allylic organometallic way to control acyclic stereochemistry and its application to the synthesis of carbohydrates , 1985 .

[26]  M. Neuenschwander,et al.  Chloracylierung und Bromacylierung von Carbonylverbindungen: Eine in Vergessenheit geratene Carbonylreaktion. I. Präparative Anwendungsbreite , 1978 .

[27]  W. C. Still,et al.  Allyloxycarbanions. A synthesis of 3,4-dihydroxy-1-olefins from carbonyl compounds , 1976 .

[28]  W. C. Still,et al.  Allyloxy carbanions. New synthesis of aldehydes via a .beta.-acyl carbanion equivalent , 1974 .

[29]  Davidr . Evans,et al.  Metalated allylic ethers as homoenolate anion equivalents , 1974 .