Diastereoselective palladium-catalyzed formate reduction of allylic carbonates as a new entry into propionate units.

[reaction: see text] The diastereoselective palladium-catalyzed formate reduction of allylic carbonates is described. Reduction of allylic carbonates under mild conditions (Pd(OAc)(2) (2.5-5 mol %), [n-Bu(3)PH]BF(4) (2.5-5 mol %), HCO(2)H/Et(3)N (1:2) (3 equiv), CH(3)CN (0.05M), 40 degrees C) affords the terminal olefin as the syn isomer in good yields and modest to excellent diastereoselectivity. These compounds, which are useful building blocks for the synthesis of polypropionate units, are the synthetic equivalent of the products obtained from an aldol reaction of an alpha-methyl-beta,gamma-unsaturated aldehyde.

[1]  G. Bouchain,et al.  Total synthesis of ionomycin using ring-opening strategies. , 2002, Organic letters.

[2]  Matthew L. Maddess,et al.  Enantioselective allylation of beta,gamma-unsaturated aldehydes generated via Lewis acid induced rearrangement of 2-vinyloxiranes. , 2002, Organic letters.

[3]  G. C. Fu,et al.  Air-stable trialkylphosphonium salts: simple, practical, and versatile replacements for air-sensitive trialkylphosphines. Applications in stoichiometric and catalytic processes. , 2001, Organic letters.

[4]  Ping Liu,et al.  Total synthesis of (+)-ambruticin S. , 2001 .

[5]  Hoffmann,et al.  Conformation Design of Open-Chain Compounds. , 2000, Angewandte Chemie.

[6]  Tamio Hayashi,et al.  Chiral monodentate phosphine ligand MOP for transition-metal-catalyzed asymmetric reactions. , 2000, Accounts of chemical research.

[7]  I. Shimizu,et al.  Synthesis and properties of (η3-1-methylallyl)palladium(II) formates as models of intermediates in the palladium-catalyzed reductive cleavage of allylic carboxylates and carbonates with formic acid , 2000 .

[8]  M. Lautens,et al.  Use of γ-Carboxy-α,β-unsaturated Aldehydes as Synthetic Equivalents of β,γ-Unsaturated Aldehydes in a Novel Stereoselective Approach to Diketides , 2000 .

[9]  Tamio Hayashi.  Catalytic asymmetric reactions via π-allylpalladium complexes coordinated with chiral monophosphine ligands ☆ , 1999 .

[10]  Y. Uozumi,et al.  CATALYTIC ASYMMETRIC SYNTHESIS OF OPTICALLY ACTIVE ALKENES BY PALLADIUM-CATALYSED ASYMMETRIC REDUCTION OF RACEMIC ALLYLIC ESTERS WITH FORMIC ACID , 1996 .

[11]  K. Yanagi,et al.  Catalytic Asymmetric Reduction of Allylic Esters with Formic Acid Catalyzed by Palladium-MOP Complexes , 1994 .

[12]  J. Tsuji,et al.  Highly active Pd(O) catalyst from Pd(OAc)2Bu3P combination in untapped 1:1 ratio: Preparation, reactivity, and 31P-NMR , 1993 .

[13]  J. Tsuji,et al.  Stereocontrolled formation of cis and trans ring junctions in hydrindane, decalin, and steroid systems by palladium-catalyzed regioselective and stereospecific hydrogenolysis of allylic formates , 1993 .

[14]  J. Tsuji,et al.  A simple preparative method for isopropenyl and vinyl groups from ketones , 1992 .

[15]  R. Bloch,et al.  Endo-2-methyl-bicyclo[2.2.1]-hept-5enyl ethyl ketone: an useful and highly stereoselective synthon for aldol reactions , 1992 .

[16]  J. Tsuji,et al.  Stereocontrolled formation of cis and trans ring junctions in hydrindane and decalin systems by palladium-catalyzed regioselective and stereospecific hydrogenolysis of allylic formates , 1992 .

[17]  W. Roush.  CONCERNING THE DIASTEREOFACIAL SELECTIVITY OF THE ALDOL REACTIONS OF ALPHA-METHYL CHIRAL ALDEHYDES AND LITHIUM AND BORON PROPIONATE ENOLATES , 1991 .

[18]  I. Shimizu,et al.  Synthesis and properties of (π-allyl)palladium formates as intermediates in palladium-catalyzed reductive cleavage of allylic acetates and carbonates with formic acid , 1991 .

[19]  H. Yamazaki,et al.  Palladium-catalyzed selective hydrogenolysis of alkenyloxiranes with formic acid. Stereoselectivity and synthetic utility , 1989 .

[20]  E. Keinan,et al.  Selective deoxygenation of unsaturated carbohydrates with Pd(0)/Ph2SiH2/ZnCl2. Total synthesis of (+)-(S,S)-(6-methyltetrahydropyran-2-yl)acetic acid , 1988 .

[21]  I. Shimizu,et al.  Palladium-Catalyzed Selective Hydrogenolysis of Alkenylcyclopropanes Having Two Electron Withdrawing Groups Using Ammonium Formates , 1988 .

[22]  I. Minami,et al.  Preparation of 1-Alkenes by the Palladium-Catalyzed Hydrogenolysis of Terminal Allylic Carbonates and Acetates with Formic Acid-Triethylamine , 1986 .

[23]  I. Shimizu,et al.  Stereoselective Synthesis of (E)-5-Hydroxy-4-methyl-2-alkenoates by Palladium-Catalyzed Stereospecific Hydrogenolysis of (E)-4,5-Epoxy-4-methyl-2-alkenoates with Ammonium Formate , 1986 .

[24]  I. Minami,et al.  REGIOSELECTIVE SYNTHESIS OF 1-OLEFINS BY PALLADIUM-CATALYZED HYDROGENOLYSIS OF TERMINAL ALLYLIC COMPOUNDS WITH AMMONIUM FORMATE , 1984 .

[25]  J. Baeckvall.  Palladium in some selective oxidation reactions , 1983 .

[26]  R. O. Hutchins,et al.  Regio- and stereoselective reductive replacement of allylic oxygen, sulfur, and selenium functional groups by hydride via catalytic activation by palladium(0) complexes , 1982 .

[27]  J. Tsuji,et al.  A convenient method for the preparation of 1-olefins by the palladium catalyzed hydrogenolysis of allylic acetates and allylic phenyl ethers with ammonium formate , 1979 .

[28]  I. Yosioka,et al.  Pyxinic acid, a novel lichen triterpene with 3β-hydroxyl function , 1966 .