Application of N,S-chelating chiral zinc bis(arenethiolate) complexes as new precursor catalysts in the enantioselective addition of diethylzinc to aldehydes

Rijnberg, Evelien; Jastrzebski, Johann T. B. H.; Janssen, Maurits D.; Boersma, J.; Koten, Gerard van

doi:10.1016/s0040-4039(00)78262-1

Cited by 68 publications

(23 citation statements)

References 11 publications

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“…4 Very recently, we have also found that zinc(II) arenethiolate complexes can be used as catalysts in the enantioselective addition of ZnR 2 to various aldehydes. 5 To understand the coordination behavior and reactivity of arenethiolate ligands with potentially coordinating donor substituents, we have isolated the corresponding lithium complexes and studied their structure and reactivity. Here, we report the syntheses of lithium complexes containing such ligands ( Figure 1) and show how the positioning of the intramolecularly coordinating functions can affect their aggregation state and structure.…”

Section: Introductionmentioning

confidence: 99%

Structural Aspects of Lithium Arenethiolate Complexes with Intramolecular Coordinating Amine Donors

et al. 1996

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Reaction of aryllithium reagents LiR (R = C6H4((R)-CH(Me)NMe2)-2 (1a), C6H3(CH2NMe2)2-2,6 (1b), C6H4(CH2N(Me)CH2CH2OMe)-2 (1c)) with 1 equiv of sulfur (1/8 S8) results in the quantitative formation of the corresponding lithium arenethiolates [Li{SC6H4((R)-CH(Me)NMe2)-2}]6 (3), [Li{SC6H3(CH2NMe2)2-2,6}]6 (4), and [Li{SC6H4(CH2N(Me)CH2CH2OMe)-2}]2 (5). Alternatively, 3 can be prepared by reacting the corresponding arenethiol HSC6H4((R)-CH(Me)NMe2)-2 (2) with nBuLi. X-ray crystal structures of lithium arenethiolates 3 and 4, reported in abbreviated form, show them to have hexanuclear prismatic and hexanuclear planar structures, respectively, that are unprecedented in lithium thiolate chemistry. The lithium arenethiolate [Li{SC6H4(CH2N(Me)CH2CH2OMe)-2}]2 (5) is dimeric in the solid state and in solution, and crystals of 5 are monoclinic, space group P21/c, with a = 17.7963(9) Å, b = 8.1281(7) Å, c = 17.1340(10) Å, β = 108.288(5)°, Z = 4, and final R = 0.047 for 4051 reflections with F > 4σ(F). Hexameric 4 reacts with 1 equiv of lithium iodide and 2 equiv of tetrahydrofuran to form the dinuclear adduct [Li2(SAr)(I)(THF)2] (6). Crystals of 6 are monoclinic, space group P21/c, with a = 13.0346(10) Å, b = 11.523(3) Å, c = 16.127(3) Å, β = 94.682(10)°, Z = 4, and final R = 0.059 for 3190 reflections with F > 4σ(F).

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Section: Introductionmentioning

confidence: 99%

Structural Aspects of Lithium Arenethiolate Complexes with Intramolecular Coordinating Amine Donors

et al. 1996

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“…[139,140] The catalytic asymmetric addition of these reagents to aldehydes using van Kotens amine 121 [141] ( Figure 4) afforded allylic alcohols derived from terminal and internal alkynes (Scheme 52). [139,140] The catalytic asymmetric addition of these reagents to aldehydes using van Kotens amine 121 [141] ( Figure 4) afforded allylic alcohols derived from terminal and internal alkynes (Scheme 52).…”

Section: Aldol Reactionsmentioning

confidence: 99%

“…In 1998, Wipf et al, described a new procedure for the preparation of (alkenyl)(alkyl)zinc reagents 145 involving hydrozirconation instead of hydroboration (Scheme 52). [139,140] The catalytic asymmetric addition of these reagents to aldehydes using van Kotens amine 121 [141] ( Figure 4) afforded allylic alcohols derived from terminal and internal alkynes (Scheme 52).…”

Section: Aldol Reactionsmentioning

confidence: 99%

Catalytic Asymmetric Synthesis of Allylic Alcohols and Derivatives and their Applications in Organic Synthesis

2013

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Allylic alcohols represent an important and highly versatile class of chiral building blocks for organic synthesis. This Review summarizes the plethora of methods developed for the catalytic asymmetric synthesis of enantioenriched allylic alcohols. These include: dynamic kinetic resolution (DKR/DKAT), nucleophilic 1,2-addition to carbonyl groups, allylic substitution, oxidation of C-H bonds, the addition of O nucleophiles to π systems, reduction of unsaturated carbonyl compounds, and an alternative route from enantioenriched propargylic alcohols. Furthermore, these catalytic asymmetric processes are exemplified by their applications in the syntheses of complex molecules such as natural products and potential therapeutic agents.

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“…chiral bisphosphines, 2,3 which can be used as ligands in asymmetric catalysis. 4 The zinc-mediated addition of alkylzinc compounds to aldehydes, using chiral amino alcohols 5 or amino thiols 6,7 as catalyst precursors, affords the corresponding alcohols in high enantiomeric purity and high chemical yield. Recently, this methodology has been applied to the synthesis of C 2 -symmetric diols derived from terephthaldehyde and isophthaldehyde using (1S,2R)-DBNE 1 or (1S,2R)-PHONE as catalyst precursors.…”

mentioning

confidence: 99%

“…) and the aminoarenethiolate-based catalyst precursors (2-3b 6,7 ) (see Fig. 1) were applied in this reaction.…”

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Enantioselective dialkylation of 1,2-phthalicdicarboxaldehyde

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et al. 2001

Tetrahedron Letters

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Application of N,S-chelating chiral zinc bis(arenethiolate) complexes as new precursor catalysts in the enantioselective addition of diethylzinc to aldehydes

Cited by 68 publications

References 11 publications

Structural Aspects of Lithium Arenethiolate Complexes with Intramolecular Coordinating Amine Donors

Structural Aspects of Lithium Arenethiolate Complexes with Intramolecular Coordinating Amine Donors

Catalytic Asymmetric Synthesis of Allylic Alcohols and Derivatives and their Applications in Organic Synthesis

Enantioselective dialkylation of 1,2-phthalicdicarboxaldehyde

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