A straightforward synthesis of 1,3-dichloro-5,8-dihydroisoquinoline by consecutive Stille cross-coupling and metathesis reactions

Hoogenband, Adri van den; Hartog, J.; Faber-Hilhorst, Nancy; Lange, Jos H.M.; Terpstra, Jan Willem

doi:10.1016/j.tetlet.2009.06.101

Cited by 16 publications

(15 citation statements)

References 43 publications

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“…This is consistent with the aza-allyl coordination mode, as depicted in Scheme 2. The calcium-oxygen bond lengths are 2.3957(16) (Ca1-O3), 2.4358(16) (Ca1-O2), and 2.4001(16) (Ca1-O1) and compare well with the Ca-O distances in 9 a·A C H T U N G T R E N N U N G (THF) 4 (see Figure 2) and similar compounds. [31] The calcium center is drawn out of the O1-O2-O3 plane by 0.5928 (4) .…”

supporting

confidence: 55%

“…Again, the reaction proceeded with complete regioselectivity to afford the 1-allylated isoquinoline derivative. Single crystals of 9 a·A C H T U N G T R E N N U N G (THF) 4 suitable for X-ray diffraction experiments were obtained from a cooled solution of 9 a·A C H T U N G T R E N N U N G (THF) 3 in THF containing triglyme as an additive. To the best of our knowledge, 9 a·A C H T U N G T R E N N U N G (THF) 4 is the first example of a structurally characterized 1-substituted and dearomatized isoquinoline derivative.…”

Section: Isoquinoline (9)mentioning

confidence: 99%

“…In the latter case, attaching activating substituents is crucial for further transformations. The introduction of olefinic functionalities such as vinyl or allyl substituents results in valuable starting materials for ring-closing metathesis, [4] epoxidation/dihydroxylation, [5] cyclopropanation, [5b] and polymerization [6] reactions. Cross-coupling reactions, including Hiyama, [7] Kumada, [8] Negishi, [9] Stille, [10] and SuzukiMiyaura [11] reactions, have broadened the scope of applications of substituent modification reactions.…”

Section: Introductionmentioning

confidence: 99%

“…9 a·A C H T U N G T R E N N U N G (THF) 4 and 4 b·-A C H T U N G T R E N N U N G (THF) 3 were additionally characterized in the solid state by X-ray diffraction experiments. 4 b·A C H T U N G T R E N N U N G (THF) 3 shows an azaallyl coordination mode in the solid state.…”

Section: Introductionmentioning

confidence: 99%

“…The bond lengths of 2.846(3) (Ca1-C6) and 2.813(3) (Ca1-C13) lie in the range of calcium-carbon bonds observed for the triglyme adduct of bisA C H T U N G T R E N N U N G (h 3 -allyl)calcium and exclude s-bound carbanionic ligands. [24] The Ca1-N1 and Ca1-N2 bond lengths of 2.407(2) and 2.4331 (19) are somewhat longer than those in 9 a·A C H T U N G T R E N N U N G (THF) 4 …”

mentioning

confidence: 97%

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Calcium‐Mediated Dearomatization, CH Bond Activation, and Allylation of Alkylated and Benzannulated Pyridine Derivatives

Jochmann

Leich

Spaniol

et al. 2011

Chemistry A European J

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A facile and general synthetic pathway for the production of dearomatized, allylated, and C-H bond activated pyridine derivatives is presented. Reaction of the corresponding derivative with the previously reported reagent bis(allyl)calcium, [Ca(C(3)H(5))(2)] (1), cleanly affords the product in high yield. The range of N-heterocyclic compounds studied comprised 2-picoline (2), 4-picoline (3), 2,6-lutidine (4), 4-tert-butylpyridine (5), 2,2'-bipyridine (6), acridine (7), quinoline (8), and isoquinoline (9). Depending on the substitution pattern of the pyridine derivative, either carbometalation or C-H bond activation products are obtained. In the absence of methyl groups ortho or para to the nitrogen atom, carbometalation leads to dearomatized products. C(sp(3))-H bond activation occurs at ortho and para situated methyl groups. Steric shielding of the 4-position in pyridine yields the ring-metalated product through C(sp(2))-H bond activation instead. The isolated compounds [Ca(2-CH(2)-C(5)H(4)N)(2)(THF)] (2b⋅(THF)), [Ca(4-CH(2)-C(5)H(4)N)(2)(THF)(2)] (3b⋅(THF)(2)), [Ca(2-CH(2)-C(5)H(3)N-6-CH(3))(2)(THF)(n)] (4b⋅(THF)(n); n=0, 0.75), [Ca{2-C(5)H(3)N-4-C(CH(3))(3)}(2)(THF)(2)] (5c⋅(THF)(2)), [Ca{4,4'-(C(3)H(5))(2)-(C(10)H(8)N(2))}(THF)] (6a⋅(THF)), [Ca(NC(13) H(9)-9-C(3)H(5))(2)(THF)] (7a⋅(THF)), [Ca(4-C(3) H(5)-C(9) H(7)N)(2)(THF)] (8b⋅(THF)), and [Ca(1-C(3)H(5)-C(9)H(7) N)(2)(THF)(3)] (9a⋅(THF)(3)) have been characterized by NMR spectroscopy and metal analysis. 9a⋅(THF)(4) and 4b⋅(THF)(3) were additionally characterized in the solid state by X-ray diffraction experiments. 4b⋅(THF)(3) shows an aza-allyl coordination mode in the solid state. Based on the results, mechanistic aspects are discussed in the context of previous findings.

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supporting

confidence: 55%

Section: Isoquinoline (9)mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 97%

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Calcium‐Mediated Dearomatization, CH Bond Activation, and Allylation of Alkylated and Benzannulated Pyridine Derivatives

Jochmann

Leich

Spaniol

et al. 2011

Chemistry A European J

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Olefin Ring‐Closing Metathesis

Yet

2016

Organic Reactions

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The olefin ring‐closing metathesis reaction catalyzed by ruthenium and molybdenum complexes has been employed in the syntheses of carbocycles, heterocycles, supramolecular compounds, and in tandem metathesis reactions. Chiral ruthenium and molybdenum catalysts have provided high enantiomeric and diastereomeric excesses in ring‐closing metathesis reactions. Many of the unsuccessful medium‐ and large‐sized ring formations which were unsuccessful by traditional methods, such as the intramolecular Wittig, Horner–Wadsworth–Emmons, and Julia–Kocienski reactions, can now be formed by olefin ring‐closing metathesis reactions. Ring‐closing metathesis has been a key step and sometimes the only successful method for the synthesis of numerous natural products and drug discovery targets. The objective of this chapter is to provide an updated, comprehensive coverage of the literature of the olefin ring‐closing metathesis reaction and related processes. Key mechanistic points are summarized.

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Partially Saturated Bicyclic Heteroaromatics as an sp³‐Enriched Fragment Collection

et al. 2016

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A straightforward synthesis of 1,3-dichloro-5,8-dihydroisoquinoline by consecutive Stille cross-coupling and metathesis reactions

Cited by 16 publications

References 43 publications

Calcium‐Mediated Dearomatization, CH Bond Activation, and Allylation of Alkylated and Benzannulated Pyridine Derivatives

Calcium‐Mediated Dearomatization, CH Bond Activation, and Allylation of Alkylated and Benzannulated Pyridine Derivatives

Olefin Ring‐Closing Metathesis

Partially Saturated Bicyclic Heteroaromatics as an sp³‐Enriched Fragment Collection

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A straightforward synthesis of 1,3-dichloro-5,8-dihydroisoquinoline by consecutive Stille cross-coupling and metathesis reactions

Cited by 16 publications

References 43 publications

Calcium‐Mediated Dearomatization, CH Bond Activation, and Allylation of Alkylated and Benzannulated Pyridine Derivatives

Calcium‐Mediated Dearomatization, CH Bond Activation, and Allylation of Alkylated and Benzannulated Pyridine Derivatives

Olefin Ring‐Closing Metathesis

Partially Saturated Bicyclic Heteroaromatics as an sp3‐Enriched Fragment Collection

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Partially Saturated Bicyclic Heteroaromatics as an sp³‐Enriched Fragment Collection