Grignard-type carbonyl addition of allyl halides by means of chromous salt. A chemospecific synthesis of homoallyl alcohols

Okude, Yoshitaka; Hirano, S.; Hiyama, Tamejiro; Nozaki, Hitosi

doi:10.1021/ja00451a061

Cited by 483 publications

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“…Therefore, Kishi and I sent both our manuscripts to the editor of JACS asking that the two be printed back to back. 17,19 This alkenylation reaction, sometimes called the NHK (NozakiHiyamaKishi) reaction 20 is different from the chromium-mediated allylation (NozakiHiyama reaction) 11 because the allylation reaction proceeds without addition of a nickel catalyst. Therefore, the two reactions, alkenylation and allylation, should be clearly distinguished.…”

Section: 15mentioning

confidence: 99%

“…In 1977, Hiyama and Nozaki reported a convenient preparation of chromium(II) species in aprotic solvents: reduction of chromium(III) chloride with 0.5 molar equivalent of LiAlH 4 in THF. 11 The anhydrous chromium(II) species enabled the reduction of a geminal dibromocyclopropane moiety on an 8-membered ring to give the corresponding allene in quantitative yield. 12 The anhydrous chromium(II) species could also be employed to reduce allylic halides to furnish allylic chromium reagents, which add to carbonyl compounds to give homoallylic alcohols in a stereo-and chemoselective manner.…”

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Trace Amounts of Second Metal Elements Can Play a Key Role in the Generation of Organometallic Compounds

Takai

2015

Bulletin of the Chemical Society of Japan

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). He has developed several synthetic methods using early transition metals such as chromium, titanium, and tantalum. Current research in his group is aimed towards the use of the complexes of group 7 metals as catalysts in organic synthesis and C-H activation initiated by insertion of transition metals into heteroatom-hydrogen bonds. AbstractDuring the development of new synthetic organic reactions by the use of group 47 metals, we twice encountered a reproducibility problem. The key factor was trace amounts of second metal elements that contaminated the first, main metals, i.e., nickel in chromium and lead in zinc. We had determined the standard procedures for these reactions and they were adopted in Organic Syntheses. The difference in the source of zinc, i.e., contamination by a catalytic amount of lead, proved to affect both the reactivity of the SimmonsSmith reaction and the formation of alkylzinc from the corresponding iodides. By using the concept of catalytic effects of the second metals, we developed a method to use manganese metal and applied this to sequential radical and anionic reactions. In addition, allylic aluminum species were prepared smoothly from allylic halides and aluminum by addition of an indium salt, the second element. In this account, I describe how the synthetic methods were discovered and developed, with an emphasis on the stories behind the communications and articles.

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Section: 15mentioning

confidence: 99%

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confidence: 99%

Trace Amounts of Second Metal Elements Can Play a Key Role in the Generation of Organometallic Compounds

Takai

2015

Bulletin of the Chemical Society of Japan

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“…The Nozaki-Hiyama reaction is mainly applied to aldehydes but ketones can be used in some cases and the reaction can be also extended to other organochromium reagents. This reaction has been widely employed in natural product synthesis, becoming the key step in some synthesis plans and it played a key role, for example, in the highly stereocontrolled synthesis of the aliphatic segment of the antibiotic rifamycin S [1][2][3][4][5].…”

Section: Introductionmentioning

confidence: 99%

Addition of Organochromium Reagents to Heteroaryl Aldehydes. Synthesis of Heteroaryl Substituted bis-Allyl Ethers and Homoallyl Ethers

Servi

Topaloğlu²

2004

Molecules

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Heteroaryl substituted allyl and homoallyl alcohols were synthesised with two different method. Synthesis of bis-allyl ethers and homoallyl ethers were carried out via reaction of allyl bromide with allyl alcohols and homoallyl alcohols, respectively. [2.3]-Wittig Rearrangement reactions of heteroaryl substituted bis-allyl ethers were investigated using GC/MS techniques. In these reactions two unexpected products were isolated in high yield.

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“…Allylic and benzylic halides were reduced with chromium(II) salts in aprotic solvents to furnish allyl-and benzylchromium compounds, respectively, which could then undergo homocoupling.7~ In the presence of electrophiles like carbonyl compounds, the resultant allylic chromium species could be trapped to give homoallylic alcohols.6~ Allylic chromium reagents derived by reduction of allylic halides with the chromium(II) species, add to carbonyl compounds in a chemoselective manner, i.e., the reagents prefer the carbonyl groups of aldehydes to those of ketones or esters eq. [6]. In addition, organochromium compounds that contain keto, ester, or cyano groups can be prepared.…”

Section: Introductionmentioning

confidence: 99%

Nucleophilic addition of organochromium reagents to carbonyl compounds

Takai

Nozaki²

2000

Proceedings of the Japan Academy. Ser. B: Physical and Biologic

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Abstract:One important theme in organic synthesis is to accomplish highly selective transformations under mild conditions, which yield only desirable products. During the past two decades, we have developed several useful tools to achieve this, i.e., organochromium reagents. This review focuses on the following themes: 1) The historical background of organochromium reagents.2) The development of the allylic chromium reagent (Nozaki-Hiyama reaction). 3) Nickel-catalyzed addition of alkenyl-, aryl-, and alkynyl halides to aldehydes (Nozaki-Hiyama-Kishi (NHK) reaction). 4) Wittig-type olefination with geminal dichromium reagents. 5) Representative applications of organochromium reagents to the total syntheses of biologically active compounds.

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Grignard-type carbonyl addition of allyl halides by means of chromous salt. A chemospecific synthesis of homoallyl alcohols

Cited by 483 publications

References 0 publications

Trace Amounts of Second Metal Elements Can Play a Key Role in the Generation of Organometallic Compounds

Trace Amounts of Second Metal Elements Can Play a Key Role in the Generation of Organometallic Compounds

Addition of Organochromium Reagents to Heteroaryl Aldehydes. Synthesis of Heteroaryl Substituted bis-Allyl Ethers and Homoallyl Ethers

Nucleophilic addition of organochromium reagents to carbonyl compounds

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