Synthesis of 3-alkoxycarbonyl-1β-methylcarbapenem using palladium-catalyzed amidation of vinyl halide

Kozawa, Yuji; Mori, Miwako

doi:10.1016/s0040-4039(01)02091-3

Cited by 51 publications

(14 citation statements)

References 22 publications

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“…[15] More recently, the palladiumcatalyzed amination of vinyl sulfonates has also been reported. [16] A major research theme in our group over the years has been the synthesis and applications of simple and cross-conjugated enamines (2-amino-1,3-dienes).…”

Section: Introductionmentioning

confidence: 99%

Palladium‐Catalyzed Cross‐Coupling Reactions of Amines with Alkenyl Bromides: A New Method for the Synthesis of Enamines and Imines

Barluenga

Fernández

Aznar

et al. 2004

Chemistry A European J

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The palladium-catalyzed cross-coupling reaction of alkenyl bromides with secondary and primary amines gives rise to enamines and imines, respectively. This new transformation expands the applicability of palladium-catalyzed C-N bond forming reactions (the Buchwald-Hartwig amination), which have mostly been applied to aryl halides. After screening of different ligands, bases, and solvents, the catalytic combination [Pd(2)(dba)(3)]/BINAP in the presence of NaOtBu in toluene gave the best results in the cross-coupling of secondary amines with 1-bromostyrene (dba=dibenzylideneacetone, BINAP=2,2'-bis(diphenylphosphino)-1,1'-binaphthyl). The corresponding enamines are obtained cleanly and in nearly quantitative yields. However, steric hindrance seems to be a limitation of the reaction, as amines carrying large substituents are not well converted. The same methodology can be applied to the coupling of secondary amines with 2-bromostyrene. Moreover, the reaction with substituted 2-bromopropenes allows regioselective synthesis of isomerizable terminal enamines without isomerization of the double bond. The best catalytic conditions for the cross-coupling of 1-bromostyrene with primary amines include again the use of the Pd(0)/BINAP/NaOtBu system. The reaction gives rise to the expected imines in very short times and with low catalyst loadings. A set of structurally diverse imines can be prepared by this methodology through variations in the structure of both coupling partners. However, 2-bromostyrene failed to give good results in this coupling reaction, probably due to product inhibition of the catalytic cycle. Competition experiments of vinyl versus aryl amination reveal that the reaction occurs preferentially on vinyl bromides.

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Section: Introductionmentioning

confidence: 99%

Palladium‐Catalyzed Cross‐Coupling Reactions of Amines with Alkenyl Bromides: A New Method for the Synthesis of Enamines and Imines

Barluenga

Fernández

Aznar

et al. 2004

Chemistry A European J

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“…For example, Porco and co-workers synthesized several antitumor macrolides [4] and antibiotics [5] by coppermediated vinylic substitution, and Kozawa and Mori prepared a carbapenem derivative by intramolecular palladium-catalyzed coupling of a b-lactam with a vinyl bromide. [6] On the other hand, we have been interested in the introduction of various carbon substituents (such as acyl, [7] alkyl [8] or aryl [9] groups) on the nitrogen atom of sulfoximines. [10] The resulting compounds can then, for instance, be used as benzothiazine building blocks [11] or incorporated (as pseudo-b-amino acids) in peptidic chains.…”

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confidence: 99%

A General Copper‐Promoted Coupling of Sulfoximines with Vinyl Bromides

Dehli

Bolm

2005

Adv Synth Catal

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“…1 Ethyl (2E,4S,5S,6E,8E)-2-Bromo-4,5-dihydroxy-4,5-O,O-isopropylidene-9-(methoxycarbonyl)-6-methylnona-2,6,8trienoate (40) According to the general olefination procedure, a 57:32:9:2 mixture of 6b/7b/52/49 [1.057 g, containing 53.2 wt% 6b: 562.3 mg, 1.409 mmol, 0.71 equiv; 35.7 wt% 7b : 377.3 mg, 789.4 mmol, 0.40 equiv; 9.4 wt% 52: 99.4 mg, 221 mmol, 0.11 equiv; 1.7 wt% 49: 18.0 mg, 50.7 mmol, 0.025 equiv (total: 1.2 equiv); 2.2 mmol 6b/7b/52/49 per g mixture], NaH (60% in mineral oil, 63.8 mg, 1.59 mmol, 0.80 equiv) and methyl (2E,4E,6S,7R)-6,7-dihydroxy-6,7-O,O-isopropylidene-5-methyl-8-oxoocta-2,4-dienoate 27 (39; 506.8 mg, 1.993 mmol) were reacted for 90 min in THF (25 mL). Flash chromatography [∆ 5.5 cm, h 20 cm, cyclohexane-EtOAc, 10:1 (3300 mL), 1-26 (100 mL), 40 and 2-chloro-2-debromo-40: [11][12][13][14][15][16][17][18][19][20][21][22] provided the title compound 40 and its chlorine analogue (651.1 mg, 81%, 40:2-chloro-2-debromo-40 = 93:7 mol:mol) as a colorless oil. The E:Z ratio of 40 prior to chromatography was 98:2 according to 1 H NMR spectroscopy; R f = 0.65 (cyclohexane-EtOAc, 1:1); [a] D equiv); 2.3 mmol 6b/7b per g mixture], NaH (60% in mineral oil, 24.4 mg, 611 mmol, 1.0 equiv) and (R)-3-(benzyloxycarbonylamino)-4-methylpentanal 29 (43; 152.2 mg, 610.5 mmol) were reacted for 30 min in THF (10 mL).…”

Section: Ethyl 2-bromo-4-methylpent-2-enoate (32)mentioning

confidence: 99%

“…3d,5 In addition, a-bromoacrylates were converted into 1,3-dienes by reduction of the ester moiety, further olefination, and C,C coupling. 6 Apart from that, a-bromoacrylates were used in Diels-Alder reactions, 7 tandem Michael additions/cyclizations (→ aziridines, cyclopropanes, benzotetrahydrofurans, pyroglutamates), 8 radical cyclizations, 9 dehydrobrominations (→ alkynoic acids 10 ) as well as for carbapenem 11 and other natural product syntheses. 12 Almost all applications of a-bromoacrylates hinge on their being stereopure.…”

mentioning

confidence: 99%

Stereoselective Preparation of (E)-α-Bromoacrylates from Mixtures of Brominated Ando Phosphonates

Olpp¹,

Brückner²

2004

Synthesis

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E ) -a -B r o m o a c r y l a t e s f r o m A n d o P h o s p h o n a t e sAbstract: We prepared 69:31-11:89 mixtures of phosphonates 6b and 7b containing two phenoxy substituents, a CO 2 Et group, and 1 or 2 bromine atoms, respectively, at the interspersed methylene group. Deprotonating 64:36 mixtures of these reagents with NaH and adding a variety of aldehydes at 0°C provided unsaturated abromoesters. Yields were typically 70-99% and E-selectivities (i.e. ester and b-substituent cis) 80:20-98:2. Similarly, we proceeded via the chlorinated phosphonate 49 to the unsaturated a-chloroester 51 with E:Z = 94:6 (80%).The stereoselective synthesis of olefins, especially of olefins with a trisubstituted double bond, is an area of ongoing interest. 1 a-Brominated a,b-unsaturated esters ('abromoacrylates') -besides many other compounds -turn out to be versatile precursors for the construction of such olefins. This is because their C sp2 -Br bond has been engaged in many transition metal-catalyzed C,C bond forming reactions 2 such as Stille couplings, 3 Suzuki couplings, 3b,d Sonogashira couplings, 4 and copper-catalyzed trifluoromethylations. 3d,5 In addition, a-bromoacrylates were converted into 1,3-dienes by reduction of the ester moiety, further olefination, and C,C coupling. 6 Apart from that, a-bromoacrylates were used in Diels-Alder reactions, 7 tandem Michael additions/cyclizations (→ aziridines, cyclopropanes, benzotetrahydrofurans, pyroglutamates), 8 radical cyclizations, 9 dehydrobrominations (→ alkynoic acids 10 ) as well as for carbapenem 11 and other natural product syntheses. 12Almost all applications of a-bromoacrylates hinge on their being stereopure. This makes accessing these compounds only worthwhile if stereocontrol is comprised. Arguably, the most important stereocontrolled syntheses of a-bromoacrylates 3a,b -and other a-brominated derivatives of a,b-unsaturated carboxylic acids e. g. 3c -constitute C 2 -extensions of aldehydes (Scheme 1). Until recently, these transformations were effected by Wittig reactions of brominated phosphoranes 1a,b if the a-bromoacrylates were to be exclusively Z-configured (i. e., ester and b-substituent trans). 13 When it sufficed that the a-bromoacrylates were preponderantly Z-configured, one could also employ the brominated phosphonates 4a,b to conduct Horner-Wadsworth-Emmons ('HWE') reactions. 14 Takai's syntheses of trans-configured 1-iodoolefins from aldehydes and iodoform 15 were extended using methyl tribromoacetate (5a) in a similar fashion, which led to brominated cinnamic esters 3a (R = anisyl, piperonyl) with very high Z-selectivity. 16 Scheme 1 C 2 -Elongating syntheses of a-bromoacrylatesThe only E-selective syntheses of methyl a-bromoacrylates 3a and the corresponding ethyl esters 3b were reported by Kogen and Tago 3d,17a,b and by Qing and Zhang, 17c respectively. The E-configured Weinreb amide analogs 3c were obtained in a similar manner by Deslongchamps et al. 17d All three groups adopted the Still-Gennari variant of the HWE reaction -starting from brom...

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Synthesis of 3-alkoxycarbonyl-1β-methylcarbapenem using palladium-catalyzed amidation of vinyl halide

Cited by 51 publications

References 22 publications

Palladium‐Catalyzed Cross‐Coupling Reactions of Amines with Alkenyl Bromides: A New Method for the Synthesis of Enamines and Imines

Palladium‐Catalyzed Cross‐Coupling Reactions of Amines with Alkenyl Bromides: A New Method for the Synthesis of Enamines and Imines

A General Copper‐Promoted Coupling of Sulfoximines with Vinyl Bromides

Stereoselective Preparation of (E)-α-Bromoacrylates from Mixtures of Brominated Ando Phosphonates

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Synthesis of 3-alkoxycarbonyl-1β-methylcarbapenem using palladium-catalyzed amidation of vinyl halide

Cited by 51 publications

References 22 publications

Palladium‐Catalyzed Cross‐Coupling Reactions of Amines with Alkenyl Bromides: A New Method for the Synthesis of Enamines and Imines

Palladium‐Catalyzed Cross‐Coupling Reactions of Amines with Alkenyl Bromides: A New Method for the Synthesis of Enamines and Imines

A General Copper‐Promoted Coupling of Sulfoximines with Vinyl Bromides

Stereoselective Preparation of (E)-α-Bromoacrylates from Mixtures of Brominated­ Ando Phosphonates

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Stereoselective Preparation of (E)-α-Bromoacrylates from Mixtures of Brominated Ando Phosphonates