Stereoselective synthesis of 1-methyl-1,2-and 1,3-cyclopentanediols via γ-lactones

Niidu, Allan; Paju, Anne; Müürisepp, Aleksander-Mati; Järving, Ivar; Kailas, Tiiu; Pehk, Tõnis; Lopp, Margus

doi:10.1007/s10593-013-1206-4

Cited by 3 publications

(4 citation statements)

References 33 publications

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“…The lack of chemoselectivity resulting from the high rates at which allylmagnesium halides react presents a problem for multiply substituted electrophiles commonly encountered in synthesis. Scheme illustrates the problematic behavior of allylmagnesium bromide compared to vinylmagnesium bromide in such a system . Addition of vinylmagnesium bromide to compound 30 , which contains both carbonyl and carboethoxy groups, resulted in addition to the carbonyl group followed by transesterification.…”

Section: Impact Of the Mechanism Of Addition Upon Stereoselectivitymentioning

confidence: 65%

“…Scheme 12 illustrates the problematic behavior of allylmagnesium bromide compared to vinylmagnesium bromide in such a system. 42 Addition of vinylmagnesium bromide to compound 30, which contains both carbonyl and carboethoxy groups, resulted in addition to the carbonyl group followed by transesterification. Conversely, allylmagnesium bromide added to both the carbonyl and carboethoxy groups of compound 30 at comparable rates.…”

Section: Diffusion-controlled Additionsmentioning

confidence: 99%

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Reactions of Allylmagnesium Reagents with Carbonyl Compounds and Compounds with C═N Double Bonds: Their Diastereoselectivities Generally Cannot Be Analyzed Using the Felkin–Anh and Chelation-Control Models

et al. 2020

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This review describes the additions of allylmagnesium reagents to carbonyl compounds and to imines, focusing on the differences in reactivity between allylmagnesium halides and other Grignard reagents. In many cases, allylmagnesium reagents either react with low stereoselectivity when other Grignard reagents react with high selectivity, or allylmagnesium reagents react with the opposite stereoselectivity. This review collects hundreds of examples, discusses the origins of stereoselectivities or the lack of stereoselectivity, and evaluates why selectivity may not occur and when it will likely occur. CONTENTS 4.2.5. Additions to β-Substituted Aldehydes 4.2.6. Additions to Aldehydes with Distant Chelating Groups 4.3. Additions to Cyclic Ketones 4.3.1. Alkoxy-Substituted Cyclic Ketones 4.3.2. Additions to Alkoxy-Substituted Five-Membered-Ring Ketones 4.3.3. Additions to Alkoxy-Substituted Four-Membered-Ring Ketones 4.4. Additions of Allylmagnesium Halides to Cyclic Hemiacetals 5. Diastereoselectivity of Reactions of Allylmagnesium Reagents with Carbonyl Compounds by Felkin−Anh Control 5.1. Felkin−Anh Stereoselectivity 5.2. Additions to α-Chiral Acyclic Ketones 5.3. Additions to Chiral Exocyclic Ketones and Aldehydes 5.4. Additions of Allylmagnesium Halides to Chiral Cyclic Ketones Controlled by Felkin−Anh Selectivity 5.5. Additions of Allylmagnesium Halides to Chiral Acyclic Aldehydes 6. Diastereoselectivity of Reactions with Carbonyl Compounds by Steric Approach Control 6.1. Steric Approach Control and Stereoselectivity

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Section: Impact Of the Mechanism Of Addition Upon Stereoselectivitymentioning

confidence: 65%

Section: Diffusion-controlled Additionsmentioning

confidence: 99%

Reactions of Allylmagnesium Reagents with Carbonyl Compounds and Compounds with C═N Double Bonds: Their Diastereoselectivities Generally Cannot Be Analyzed Using the Felkin–Anh and Chelation-Control Models

et al. 2020

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“…In a competition between an aldehyde and a sterically unhindered ester ( 1 vs 15 ), addition to the electronically stabilized ester was competitive. By comparison, MeMgCl reacted preferentially with the aldehyde, as has been observed for additions of organomagnesium reagents to substrates bearing both an aldehyde and either an ester or lactone functional group. − The fact that the rates of additions of allylmagnesium reagents are similar but alkylmagnesium reagents are different is consistent with observations that reactions of substituted aryl ketones and aldehydes with allylmagnesium reagents, unlike their alkyl partners, were insensitive to electronic effects. , Allylmagnesium reagents also did not discriminate between electrophiles bearing different kinds of carbonyl groups, unlike other nucleophiles. , …”

mentioning

confidence: 92%

“…10,32 Allylmagnesium reagents also did not discriminate between electrophiles bearing different kinds of carbonyl groups, unlike other nucleophiles. 33,34 Allylmagnesium halides were only able to differentiate between carbonyl compounds when one was considerably more sterically hindered than the other (eq 1). The addition of allylmagnesium chloride to acetophenone (2) to form product 4b was highly favored over addition to di-tert-butyl ketone (17).…”

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confidence: 99%

Allylmagnesium Halides Do Not React Chemoselectively Because Reaction Rates Approach the Diffusion Limit

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Woerpel

2017

J. Org. Chem.

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Competition experiments demonstrate that additions of allylmagnesium halides to carbonyl compounds, unlike additions of other organomagnesium reagents, occur at rates approaching the diffusion rate limit. Whereas alkylmagnesium and alkyllithium reagents could differentiate between electronically or sterically different carbonyl compounds, allylmagnesium reagents reacted with most carbonyl compounds at similar rates. Even additions to esters occurred at rates competitive with additions to aldehydes. Only in the case of particularly sterically hindered substrates, such as those bearing tertiary alkyl groups, were additions slower.

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ChemInform Abstract: Stereoselective Synthesis of 1‐Methyl‐1,2‐ and 1,3‐Cyclopentanediols via γ‐Lactones.

et al. 2013

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Stereoselective synthesis of 1-methyl-1,2-and 1,3-cyclopentanediols via γ-lactones

Cited by 3 publications

References 33 publications

Reactions of Allylmagnesium Reagents with Carbonyl Compounds and Compounds with C═N Double Bonds: Their Diastereoselectivities Generally Cannot Be Analyzed Using the Felkin–Anh and Chelation-Control Models

Reactions of Allylmagnesium Reagents with Carbonyl Compounds and Compounds with C═N Double Bonds: Their Diastereoselectivities Generally Cannot Be Analyzed Using the Felkin–Anh and Chelation-Control Models

Allylmagnesium Halides Do Not React Chemoselectively Because Reaction Rates Approach the Diffusion Limit

ChemInform Abstract: Stereoselective Synthesis of 1‐Methyl‐1,2‐ and 1,3‐Cyclopentanediols via γ‐Lactones.

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