Synthesis of 2‘-Alkylspiro[2-X-cyclohexan-1,3‘-3‘H-indole] (X = H; X = CH3) by an Unexpected Reaction between an Organomagnesium Halide and 2‘-Methylspiro[2-X-cyclohexan-1,3‘-3‘H-indole]. X-ray Structure of a Fluorescent Dimeric Compound

Rodriguez, Jorge H.; Urrutia, Anahí; Diego, J. Eugenio de; Martínez-Alcazar, ‡ and M. Paz; Fonseca, I.

doi:10.1021/jo980072x

Cited by 15 publications

(8 citation statements)

References 8 publications

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“…Additions to the indole derivative 957 provided an outcome that is difficult to accommodate by consideration of steric effects alone (Scheme ). Addition to the indoline 957 occurred smoothly with allylmagnesium iodide to give the adduct 958 . By contrast, additions of methylmagnesium iodide to indolines of this type were slow and occurred with low yields, and additions of benzylmagnesium reagents formed a number of products.…”

Section: Additions Of Allylmagnesium Reagents To Imines and Related S...mentioning

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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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: Additions Of Allylmagnesium Reagents To Imines and Related S...mentioning

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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“…18 Addition of an excess of allyl Grignard reagent yielded diamine 4 as a mixture of diastereomers. Analogous additions of methyl Grignard reagents did not produce the corresponding diamines, 19 and thus, the synthesis of diradical 1 was not feasible. In the next step, the allyl groups in 4 were catalytically reduced with H 2 to the corresponding n-propyl (n-Pr) groups in 5.…”

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confidence: 99%

Triplet Ground State Derivative of Aza-m-xylylene Diradical with Large Singlet−Triplet Energy Gap

2011

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Organic molecules with a strong preference for triplet ground states, in which the triplet state is below the lowest singlet state by ≥10 kcal/mol, are typically short-lived and mostly detected as reactive intermediates. We now report a triplet ground state derivative of aza-m-xylylene diradical with a large singlet-triplet energy gap (ΔE(ST)) of ∼10 kcal/mol, which is comparable to ΔE(ST) for the well-known reactive intermediate m-xylylene diradical. The aminyl diradical persists in solution at room temperature on the time scale of minutes.

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“…Likewise, tetrahydrobiphenylene 7 h served as a representative substrate for consecutive reactions of this substrate class. A diastereoselective cuprate addition [24] delivered saturated ketone 11, which was then subjected to a Suzuki Scheme 3. Suggested reaction pathway for the photochemical rearrangement of product 5 a to tetrahydrobiphenylene 7 a (= ^: equivalent to).…”

Section: Methodsmentioning

confidence: 99%

Enantioselective Intramolecular ortho Photocycloaddition Reactions of 2‐Acetonaphthones

Yan,

Stegbauer,

et al. 2024

Angew Chem Int Ed

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2‐Acetonaphthones, which bear an alkenyl group tethered to its C1 carbon atom via an oxygen atom, were found to undergo an enantioselective, intramolecular ortho photocycloaddition reaction. A chiral oxazaborolidine Lewis acid leads to a bathochromic absorption shift of the substrate and enables an efficient enantioface differentiation. Visible light irradiation (λ = 450 nm) triggers the reaction which is tolerant of various groups at almost any position except carbon atom C8 (16 examples, 53‐99% yield, 80‐97% ee). Consecutive reactions were explored including a sensitized rearrangement to tetrahydrobiphenylenes, which occurred with full retention of configuration. Evidence was collected that the catalytic photocycloaddition occurs via triplet intermediates, and the binding mode of the acetonaphthone to the chiral Lewis acid was elucidated by DFT calculations.

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Synthesis of 2‘-Alkylspiro[2-X-cyclohexan-1,3‘-3‘H-indole] (X = H; X = CH₃) by an Unexpected Reaction between an Organomagnesium Halide and 2‘-Methylspiro[2-X-cyclohexan-1,3‘-3‘H-indole]. X-ray Structure of a Fluorescent Dimeric Compound

Cited by 15 publications

References 8 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

Triplet Ground State Derivative of Aza-m-xylylene Diradical with Large Singlet−Triplet Energy Gap

Enantioselective Intramolecular ortho Photocycloaddition Reactions of 2‐Acetonaphthones

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