ChemInform Abstract: STEREOCHEMISTRY OF THE SIMMONS‐SMITH REACTION ON ACYCLIC ALLYLIC ALCOHOLS

Ratier, Max; Castaing, Matthias; Godet, Jean-Yves; Pereyre, Michel

doi:10.1002/chin.197836100

Cited by 10 publications

(15 citation statements)

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“…There are several demonstrations of the directing influence of the hydroxyl group for epoxidation reactions 8-10 as well as for other reactions . In one study, on the Simmons−Smith reaction with cis allylic alcohols, over 99% stereoselectivity was found …”

Section: Introductionmentioning

confidence: 99%

Oxidation of Olefins by Palladium(II). 15.¹ Oxidation of (R)-(−)-(Z)- and (R)-(+)-(E)-3-Penten-2-ol Using Several Nucleophiles To Give Chiral β-Substituted Ketones. A Method of Finding Modes of Palladation of Olefins Using Chirality Transfer

Hamed

Henry

1997

Organometallics

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The oxidation of (R)-(−)-(Z)- and (R)-(+)-(E)-3-penten-2-ol with Pd(II) using hydroxyl, methoxyl, acetate, and phenyl as nucleophiles produced β-substituted ketones. The ketone products are optically active, indicating the hydroxyl group was preferentially directing the Pd(II) to one of the two faces of the double bond in forming the initial π-complex. The absolute configuration of the product depends on the absolute configuration of the starting alcohol, the π-complex face to which the nucleophile adds, and the stereochemistry of addition. Because of steric interactions between the two terminal methyl groups, one π-complex is more stable than the other. Phenylpalladium, a reagent which is known to add syn, gave (R)-4-phenyl-2-pentanone, a result that is consistent only with syn addition to the most stable π-complex. With this information, determination of the stereochemistries of addition of the other nucleophiles is possible. In aqueous solution and methanol at low [Cl-], the 4-hydroxy, and 4-methoxy-2-pentanone products had the R configuration, indicating syn addition. These results are consistent with recent stereochemical and kinetic studies. A surprise was the finding of the R configuration, indicating syn addition, for the 4-acetoxy-2-pentanone product in acetic acid solvent. Previous kinetic studies were interpreted in terms of anti addition. Another unexpected result was the reversal of addition to anti at high [Cl-] in acetic acid. As expected, the Z-isomer gave higher degrees of chirality transfer than the E-isomer.

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Section: Introductionmentioning

confidence: 99%

Oxidation of Olefins by Palladium(II). 15.¹ Oxidation of (R)-(−)-(Z)- and (R)-(+)-(E)-3-Penten-2-ol Using Several Nucleophiles To Give Chiral β-Substituted Ketones. A Method of Finding Modes of Palladation of Olefins Using Chirality Transfer

Hamed

Henry

1997

Organometallics

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“…The stereochemical outcome of the cyclopropanations of chiral allylic alcohols has been the subject of numerous investigations and is now well-established. ,, Whereas ( Z )-substituted olefins give high syn selectivities, for the ( E )-substituted ones the syn selectivities are usually modest. A staggered model has been proposed to account for the observed diastereoselectivities.…”

mentioning

confidence: 99%

Directing Effect of a Neighboring Aromatic Group in the Cyclopropanation of Allylic Alcohols

1998

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“…3.6) [39]. In the case of 8-membered rings, where a 99.5 to 0.5 anti dr is observed (46), one must carefully consider the possible conformations of a cyclooctene. The dihedral angle h (C 1 -C 2 -C 3 -C 4 ) in cis-cyclooctene is known to be *90 o (Fig.…”

Section: Stereoselective Simmons-smith Cyclopropanations 103mentioning

confidence: 99%

“…So it is not surprising that similar stereoselectivity will be manifest in the Simmons-Smith cyclopropanation, a reaction which is known to be highly dependent on a coordinative interaction. Examination of the reaction of two isomeric 3-penten-2-ols 47 and 50 shows high diastereoselectivity which is strongly dependent on the double bond configuration (Scheme 3.20) [46]. Even though this study was preformed using a racemic mixture of alcohols, information on the relative stereochemistry is still important.…”

Section: Stereoselective Simmons-smith Cyclopropanations 103mentioning

confidence: 99%

Enantioselective [2+1] Cycloaddition: Cyclopropanation with Zinc Carbenoids

Denmark

Beutner

2001

Cycloaddition Reactions in Organic Synthesis

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ChemInform Abstract: STEREOCHEMISTRY OF THE SIMMONS‐SMITH REACTION ON ACYCLIC ALLYLIC ALCOHOLS

Cited by 10 publications

References 0 publications

Oxidation of Olefins by Palladium(II). 15.¹ Oxidation of (R)-(−)-(Z)- and (R)-(+)-(E)-3-Penten-2-ol Using Several Nucleophiles To Give Chiral β-Substituted Ketones. A Method of Finding Modes of Palladation of Olefins Using Chirality Transfer

Oxidation of Olefins by Palladium(II). 15.¹ Oxidation of (R)-(−)-(Z)- and (R)-(+)-(E)-3-Penten-2-ol Using Several Nucleophiles To Give Chiral β-Substituted Ketones. A Method of Finding Modes of Palladation of Olefins Using Chirality Transfer

Directing Effect of a Neighboring Aromatic Group in the Cyclopropanation of Allylic Alcohols

Enantioselective [2+1] Cycloaddition: Cyclopropanation with Zinc Carbenoids

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ChemInform Abstract: STEREOCHEMISTRY OF THE SIMMONS‐SMITH REACTION ON ACYCLIC ALLYLIC ALCOHOLS

Cited by 10 publications

References 0 publications

Oxidation of Olefins by Palladium(II). 15.1 Oxidation of (R)-(−)-(Z)- and (R)-(+)-(E)-3-Penten-2-ol Using Several Nucleophiles To Give Chiral β-Substituted Ketones. A Method of Finding Modes of Palladation of Olefins Using Chirality Transfer

Oxidation of Olefins by Palladium(II). 15.1 Oxidation of (R)-(−)-(Z)- and (R)-(+)-(E)-3-Penten-2-ol Using Several Nucleophiles To Give Chiral β-Substituted Ketones. A Method of Finding Modes of Palladation of Olefins Using Chirality Transfer

Directing Effect of a Neighboring Aromatic Group in the Cyclopropanation of Allylic Alcohols

Enantioselective [2+1] Cycloaddition: Cyclopropanation with Zinc Carbenoids

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Oxidation of Olefins by Palladium(II). 15.¹ Oxidation of (R)-(−)-(Z)- and (R)-(+)-(E)-3-Penten-2-ol Using Several Nucleophiles To Give Chiral β-Substituted Ketones. A Method of Finding Modes of Palladation of Olefins Using Chirality Transfer

Oxidation of Olefins by Palladium(II). 15.¹ Oxidation of (R)-(−)-(Z)- and (R)-(+)-(E)-3-Penten-2-ol Using Several Nucleophiles To Give Chiral β-Substituted Ketones. A Method of Finding Modes of Palladation of Olefins Using Chirality Transfer