THE STEREOSELECTIVE SYNTHESIS OF <scp>d</scp>-RIBULOSE

Suzuki, Keisuke; Yuki, Yo-ichi; Mukaiyama, Teruaki

doi:10.1246/cl.1981.1529

Cited by 58 publications

(7 citation statements)

References 9 publications

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“…Of the two readily separated (flash chromatography) diastereoisomeric alcohols 12 (l-configuration) and 13 (u-configuration), one is formed preferentially, depending on the organometallic compound used: with MeLi, the attack occurs preferentially from the Re-face of the aldehyde-carbonyl plane (+ 12), with MeZnCI*) from the Si-face (chemical correlation as structure proof, see below). This result is reminiscent of Mukaiyama's observation in the addition of 2-furyl-metal derivatives to glyceraldehyde acetonide [8] At this point, we have shown that the dibromide 2 can be used for a number of conversions with introduction of new substituents in the 4-position of the butanoic-acid moiety. A crucial step is the subsequent hydrogenation of the dioxinone double bond with regeneration of a stereogenic center in the 6-position of the ring.…”

Section: See the Classical Investigations Bysupporting

confidence: 71%

Reactions of Chiral 2‐(tert‐Butyl)‐2H,4H‐1,3‐dioxin‐4‐ones Bearing Functional Groups in the 6‐Position and Diastereoselective Catalytic Hydrogenation to cis‐2,6‐Disubstituted 1,3‐Dioxan‐4‐ones

Noda

Seebàch²

1987

Helvetica Chimica Acta

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(R)-5-Bromo-6-(bromomethyl)-2-(tert-butyl)-2H, 4H-1,3-dioxin-4-one (2) derived from (R)-3-hydroxybutanoic acid is used for substitutions and chain elongations at the side-chain C-atom in the 6-position of the heterocycle (43-6, 10-13). Subsequent simultaneous reductive debromination and double-bond hydrogenation (Pd/C,H,) occurs with essentially complete diastereoselectivity ( > 98 % ds), with H transfer from the face opposite to the t-Bu group (+15-20, Table 1). Hydrolytic cleavages of the dioxanones then lead to enantiomerically pure P-hydroxy-acid derivatives (overall self-reproduction of the stereogenic center of 3-hydroxybutanoic acid or alkylation in the 4-position of this acid with preservation of configuration).In the course of our work on the use of the biopolymer polyhydroxybutyrate/valerate (PHB/PHV) [ 11, we have found that it is possible to prepare non-racemic dioxinones with a pivalaldehyde-derived stereogenic center, see Scheme I [2] [3]. We describe here reactions of such dioxinones at the side chain in position 6 of the heterocyclic ring2), followed by diastereoselective catalytic hydrogenation with regeneration of a stereogenic center in that position. Thus, in the overall transformation, a hydrogen atom in the 4-position of

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Section: See the Classical Investigations Bysupporting

confidence: 71%

Reactions of Chiral 2‐(tert‐Butyl)‐2H,4H‐1,3‐dioxin‐4‐ones Bearing Functional Groups in the 6‐Position and Diastereoselective Catalytic Hydrogenation to cis‐2,6‐Disubstituted 1,3‐Dioxan‐4‐ones

Noda

Seebàch²

1987

Helvetica Chimica Acta

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“…Registry No. 2,benzenethiol,2,4,tri-tert-butylthiobenzaldehyde, 84543-57-7. Communications Total Synthesis of (-)-Pseudopterosin A Summary: Pseudopterosin A has been synthesized, in optically active form, from (S)-(-)-limonene.…”

Section: Methodsmentioning

confidence: 99%

Total synthesis of (-)-pseudopterosin A

Broka¹,

Chan²,

Peterson³

1988

J. Org. Chem.

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“…Addition of 60 (prepared quantitatively from dimethylzinc and TiC14 in CH2Clz) to the aldehyde 48 led to 63 and 64 in the ratio 92 : 65 66 a, R = nRu…”

Section: Other Organometallic Reagentsmentioning

confidence: 99%

Chelation or Non‐Chelation Control in Addition Reactions of Chiral α‐ and β‐ Alkoxy Carbonyl Compounds [New Synthetic Methods (44)]

Reetz

1984

Angew. Chem. Int. Ed. Engl.

690

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The addition of C-nucleophiles such as Grignard reagents or enolates to chiral aor p-alkoxy aldehydes or ketones creates a new center of chirality and is therefore diastereogenic. In order to control stereoselectivity, two strategies have been developed: 1) Use of Lewisacidic reagents which form intermediate chelates, these being attacked stereoselectively from the less hindered side (chelation control); 2) use of reagents incapable of chelation, stereoselective attack being governed by electronic and/or steric factors (non-chelation control). Generally, the two methods lead to the opposite sense of diastereoselectivity. It is possible to predict the outcome by careful choice of organometallic reagents containing elements such as Li, Mg, B, Si, Sn, Cu, Zn, or Ti.

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THE STEREOSELECTIVE SYNTHESIS OF d-RIBULOSE

Cited by 58 publications

References 9 publications

Reactions of Chiral 2‐(tert‐Butyl)‐2H,4H‐1,3‐dioxin‐4‐ones Bearing Functional Groups in the 6‐Position and Diastereoselective Catalytic Hydrogenation to cis‐2,6‐Disubstituted 1,3‐Dioxan‐4‐ones

Reactions of Chiral 2‐(tert‐Butyl)‐2H,4H‐1,3‐dioxin‐4‐ones Bearing Functional Groups in the 6‐Position and Diastereoselective Catalytic Hydrogenation to cis‐2,6‐Disubstituted 1,3‐Dioxan‐4‐ones

Total synthesis of (-)-pseudopterosin A

Chelation or Non‐Chelation Control in Addition Reactions of Chiral α‐ and β‐ Alkoxy Carbonyl Compounds [New Synthetic Methods (44)]

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