Applications of stoichiometric organotransition metal complexes in organic synthesis

Donohoe, Timothy J.; Harji, Rakesh R.; Moore, Peter R.; Waring, Michael J.

doi:10.1039/a706382b

Cited by 12 publications

(6 citation statements)

References 63 publications

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“…7 So, Peter made a series of cyclic allylic alcohols and then oxidised them under several different conditions (Scheme 3). 8,9 It became apparent that dichloromethane did allow hydrogen bonding between reagent and substrate but that this was quite a weak effect unable to overturn the strong (anti) bias of the allylic alcohol. However, we did get a break when we bubbled trimethylamine into a solution of OsO 4 and allylic alcohol 1 in CH 2 Cl 2 -the stereoselectivity changed and became marginally syn selective!…”

Section: The Directed Dihdyroxylation Of Allylic Alcohols and Amidesmentioning

confidence: 99%

“…Quinuclidine kept coming up as one of the best amines to use and was the one that Kevin and Jon chose to develop first by modifying a reaction that had been reported earlier, and in a different context, by Giovanni Poli. 9 The idea was that quinuclidine-N-oxide (QNO) would be introduced into a dihydroxylation reaction in dichloromethane in the presence of catalytic OsO 4 . As the reaction proceeds and the QNO is reduced, then quinuclidine is released, free to coordinate to OsO 4 and give decent levels of syn selectivity, (Figure 4).…”

Section: Scheme 12 7 How To Make the Reaction Catalytic In Osmiummentioning

confidence: 99%

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Development of the Directed Dihydroxylation Reaction

Donohoe

2002

Synlett

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The following account describes our work on the development and utilisation of the directed dihydroxylation reaction. Our preliminary thoughts and experiments are described, as is the refinement and rationalisation process that eventually led to discovery of the OsO 4 /TMEDA reagent. A comprehensive description of the directed dihydroxylation of a variety of alcohols and amides is included, together with a mechanistic interpretation of this oxidation and a guide to the use of our methodology in synthesis. 1 Background to Development of the Directed Dihydroxylation 2 The Directed Dihydroxylation of Allylic Alcohols and Amides 3 Mechanism of the OsO 4 /TMEDA Promoted Oxidation 4 Control of Stereochemistry in Acyclic Systems 5 Regioselective Directed Dihydroxylations 6 Stereoselective Oxidation of Homoallylic Alcohols and Amides 7 How to Make the Reaction Catalytic in Osmium 8 Natural Product Synthesis Using the Directed Dihydroxylation Reaction 9 Conclusion and Future Directions

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Section: The Directed Dihdyroxylation Of Allylic Alcohols and Amidesmentioning

confidence: 99%

Section: Scheme 12 7 How To Make the Reaction Catalytic In Osmiummentioning

confidence: 99%

Development of the Directed Dihydroxylation Reaction

Donohoe

2002

Synlett

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“…[1] However, most of these reactions are difficult to apply to mass production. The following facts are obstacles to the use of a stoichiometric amount of transition metal compounds in mass production.…”

Section: Introductionmentioning

confidence: 99%

The Divalent Titanium Complex Ti(O-i-Pr)4/2i-PrMgX as an Efficient and Practical Reagent for Fine Chemical Synthesis

Sato

Okamoto

2001

Adv. Synth. Catal.

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This account describes synthetic transformations of unsaturated hydrocarbons, such as alkynes, alkenes, and dienes, mediated by the divalent titanium reagent Ti(O‐i‐Pr)4/2 i‐PrMgX, which proceed via (ν 2‐alkene)‐ or (ν 2‐alkyne)‐titanium intermediates. Many of these transformations are otherwise difficult or require multi‐step reaction sequences. Since Ti(O‐i‐Pr)4 and i‐PrMgX are non‐toxic and available in bulk at low price, the reagent satisfies the qualifications for use in large‐scale synthesis. 1 Introduction 2 A General View of the Ti(O‐i‐Pr)4/2 i‐PrMgX Reagent 3 Generation of an (ν 2‐Alkyne)Ti(O‐i‐Pr)2 and its Utilization as a Vicinal Vinylic Dianion 4 Preparation of Allyl‐ and Allenyltitanium Reagents and their Synthetic Utility 4.1 Allylic Titanium Reagents 4.2 Allenylic Titanium Reagents 5 Intramolecular Nucleophilic Acyl Substitution (INAS) Reactions Mediated by Ti(O‐i‐Pr)4/2 i‐PrMgX 5.1 Scope of the Reaction 5.2 Synthetic Applications of the INAS Reaction 6 Intra‐ and Intermolecular Coupling of Olefins and Acetylenes 6.1 Intramolecular Reactions 6.2 Intermolecular Reactions 6.3 Tandem Inter‐ and Intramolecular Reactions 7 Summary and Outlook

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“…Transition-metal-mediated cyclocarbonylations have attracted a great deal of interest in recent years in catalytic as well as stoichiometric processes. − Recently, we reported on novel cyclocarbonylations of β-[(η 5 -C 5 H 5 )(CO) 2 Fe]-substituted ( Z )-enals leading to γ-lactones and γ-lactams in one-pot procedures. − These reaction cascades involve the addition of an organometallic reagent (e.g., K-Selectride, RMgCl, or RLi 6 ) or the TiCl 4 -mediated addition of electron-rich primary amines 4 to the aldehyde functionality as the initial key step. In this paper reactions of β-[(η 5 -C 5 H 5 )(CO) 2 Fe]-substituted N -sulfonyl azadienes with organolithiums and Grignard reagents furnishing 5-substituted dihydropyrrolones are presented.…”

Section: Introductionmentioning

confidence: 99%

Reactions of (η⁵-C₅H₅)(CO)₂Fe-Substituted N-Sulfonyl Azadienes with C-Nucleophiles. A Route to 5-Substituted Dihydropyrrolones

2000

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A variety of cyclic -[(η 5 -C 5 H 5 )(CO) 2 Fe]-substituted N-sulfonyl azadienes 4 were prepared: e.g., from the corresponding iron-substituted (Z)-enals and benzenesulfonamide. Reactions of these iron compounds with Grignard reagents or organolithiums gave 5-substituted R, -unsaturated N-sulfonyl γ-lactams 5. In some cases the corresponding non-N-protected 5-substituted γ-lactams 6 were isolated as well. Key steps of these reaction cascades are the initial 1,2-addition to the imine moiety and the subsequent carbonylation step. The reaction of the chromene-iron complex 4e with (allyl)MgCl gave the (η 3 -allyl)-iron-γ-lactam complex 8a with a ring-opened chromene framework. This complex was structurally characterized by X-ray analysis.

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Applications of stoichiometric organotransition metal complexes in organic synthesis

Cited by 12 publications

References 63 publications

Development of the Directed Dihydroxylation Reaction

Development of the Directed Dihydroxylation Reaction

The Divalent Titanium Complex Ti(O-i-Pr)4/2i-PrMgX as an Efficient and Practical Reagent for Fine Chemical Synthesis

Reactions of (η⁵-C₅H₅)(CO)₂Fe-Substituted N-Sulfonyl Azadienes with C-Nucleophiles. A Route to 5-Substituted Dihydropyrrolones

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Applications of stoichiometric organotransition metal complexes in organic synthesis

Cited by 12 publications

References 63 publications

Development of the Directed Dihydroxylation Reaction

Development of the Directed Dihydroxylation Reaction

The Divalent Titanium Complex Ti(O-i-Pr)4/2i-PrMgX as an Efficient and Practical Reagent for Fine Chemical Synthesis

Reactions of (η5-C5H5)(CO)2Fe-Substituted N-Sulfonyl Azadienes with C-Nucleophiles. A Route to 5-Substituted Dihydropyrrolones

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Reactions of (η⁵-C₅H₅)(CO)₂Fe-Substituted N-Sulfonyl Azadienes with C-Nucleophiles. A Route to 5-Substituted Dihydropyrrolones