Synthesis and Chemistry of Substituted 1-Azabicyclo[1.1.0]butanes

Bartnik, R.; Marchand, Alan P.

doi:10.1055/s-1997-1520

Cited by 46 publications

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“…[4] The increased reactivity of the hetero systems is due to the valence isomerization to which the bicyclo[1.1.0]butanes are prone. We now report on the first 2-phospha derivatives.…”

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confidence: 99%

“…[2] However, very few systems are known with a single heteroatom, [3] probably because of their high reactivity, which is only moderated when the heteroatom occupies a bridgehead position as in the 1-aza derivatives. [4] The increased reactivity of the hetero systems is due to the valence isomerization to which the bicyclo [1.1.0]butanes are prone. We now report on the first 2-phospha derivatives.…”

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confidence: 99%

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Valence Isomerization of 2‐Phosphabicyclo[1.1.0]butanes

et al. 2005

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The unique electronic properties of the strained bicyclo-[1.1.0]butanes [1] are enhanced by the heteroatoms in the molecular frame. Illustrative is the bond-stretch isomerization of the P 2 C 2 and P 2 B 2 bicycles.[2] However, very few systems are known with a single heteroatom, [3] probably because of their high reactivity, which is only moderated when the heteroatom occupies a bridgehead position as in the 1-aza derivatives. [4] The increased reactivity of the hetero systems is due to the valence isomerization to which the bicyclo[1.1.0]butanes are prone. We now report on the first 2-phospha derivatives.The carbene-like phosphinidene Ph-P = W(CO) 5 [5] was generated in situ by cheletropic elimination from 1 at 110 8C in toluene and then allowed to react with cyclopropene 2 a [6] (Scheme 1). This led to the desired W(CO) 5 -complexed 2-phosphabicyclo[1.1.0]butanes exo-3 a (d 31 P = À85.1 ppm) and endo-3 a (d 31 P = À36.7 ppm) [7] in a 10:9 ratio, which were isolated in 69 % yield as colorless solids. The remarkably

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“…[4] The increased reactivity of the hetero systems is due to the valence isomerization to which the bicyclo[1.1.0]butanes are prone. We now report on the first 2-phospha derivatives.…”

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Valence Isomerization of 2‐Phosphabicyclo[1.1.0]butanes

et al. 2005

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“…The reaction proceeded smoothly to furnish the desired corresponding 3-sulfenylazetidine derivatives 5a-f in 50-92% yields, as shown in Table 1. Compounds 5c-f were purified as the hydrochlorides by treatment of the crude products with 2 N HCl in Et 2 O because of their instability during chromatographic purifica- 7,25) to heterocyclic thiols and benzenethiols. The resulting anionic thio group can smoothly attack the C3 position of ABB (3) followed by cleavage of the highly strained N1-C3 s-bond to furnish each corresponding 3-sulfenylazetidine derivative.…”

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confidence: 99%

“…[1][2][3][4][5][6][7][8][9][10] Specifically, the synthetic utility of ABB (3), which must be useful for the preparation of various 1,3-disubstituted and 3-monosubstituted azetidines, 1,9,10) has scarcely reported because of its synthetic difficulty due to the remarkably strained structure. These azetidine moieties have often been found in many natural products 11) and biologically active compounds such as carbapenems 1) and new quinolone antibiotics.…”

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Synthesis of New Quinolone Antibiotics Utilizing Azetidine Derivatives Obtained from 1-Azabicyclo[1.1.0]butane

Ikee

Hashimoto

Kamino

et al. 2008

CHEMICAL & PHARMACEUTICAL BULLETIN

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Although 1-azabicyclo[1.1.0]butane (ABB, 3) proved to be the unique molecule bearing the highly strained bicyclic structure, little attention has been paid to the unusual ring system. [1][2][3][4][5][6][7][8][9][10] Specifically, the synthetic utility of ABB (3), which must be useful for the preparation of various 1,3-disubstituted and 3-monosubstituted azetidines, 1,9,10) has scarcely reported because of its synthetic difficulty due to the remarkably strained structure. These azetidine moieties have often been found in many natural products 11) and biologically active compounds such as carbapenems 1) and new quinolone antibiotics.12-15) 1,3,3-Trinitroazetidine (TNAZ), 16,17) an insensitive high explosive, was also synthesized by using ABB (3). In recent years, we established an efficient method for synthesis of ABB (3) starting from allylamine (1) via 2,3-dibromopropylamine hydrobromide (2), and reported its application to the synthesis of several azetidine derivatives, as shown in Chart 1. 9) We also reported a practical synthesis of 1-(1,3-thiazolin-2-yl)azetidine-3-thiol as the fascinating pendant moiety of a new oral 1b-methylcarbapenem antibiotic, L-084 by starting from ABB (3).1) This expeditious construction method for 3-monosubstituted azetidine derivatives employing ABB (3) seemed to be useful also for developing new quinolone antibiotics.Fluoroquinolones have been developed and are widely used clinically. This is because they have potent, a broad spectrum of antibacterial activities, and few side effects. [18][19][20][21][22] However, increasingly multidrug-resistant pathogens, especially methicillin-resistant Staphylococcus aureus (MRSA), have become a serious problem particularly during the last decade.23) The resistance levels to quinolones are as yet relatively low but are steadily increasing.24) Therefore new antibacterial agents have become increasingly urgent. This prompted us to develop new quinolones utilizing the azetidine derivatives, in which the C7 substituents of fluoroquinolone carboxylic acids play important antibacterial roles.18-22) Previously, we communicated synthesis and antibacterial activities of new quinolone derivatives utilizing ABB (3). 10)We now describe, in detail, a convenient method of synthesizing several 3-sulfenyl-and 3-aminoazetidine derivatives utilizing ABB (3), and we discuss the synthesis and antibacterial activities of new quinolone antibiotics incorporating these azetidine derivatives to the C7 position. Although several examples of 7-azetidinylquinolones have been reported, [12][13][14][15] there have been not many prominent quinolone antibiotics bearing the azetidinyl substituent groups thus far. We envisaged that the introduction of azetidine derivatives onto the C7 position of the quinolone nucleus might enhance their antibacterial activities against MRSA. Results and DiscussionA tetrahydrofuran (THF) solution of ABB (3), obtained by treatment of 2,3-dibromopropylamine hydrobromide (2) with n-BuLi at Ϫ78°C in THF followed by codistillation with THF, 1) was...

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“…Particularly important synthetic applications of 1-azabicyclo-[1.1.0]butanes include additions of reagents of the XϪY type across the highly strained NϪC(3) σ-bond, a variety of such reagents having thus been treated with 3-and 2,3-disubstituted 1-azabicyclo[1.1.0]butanes to produce corresponding substituted azetidines. [5,6] The aim of our study was to determine the structures of products formed from 1-azabicylo[1.1.0]butane under FVT conditions, by chemical trapping and by photoelectron spectroscopy. In analogy with the thermal rearrangement of bicyclo[1.1.0]butane to buta-1,3-diene, [7,8] the corresponding 2-aza-1,3-dienes would be expected.…”

Section: Introductionmentioning

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Flash Vacuum Thermolysis of 1‐Azabicyclo[1.1.0]butanes. Photoelectron Spectrum of 3‐Phenyl‐2‐azabuta‐1,3‐diene

et al. 2003

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The reaction behaviour of 1‐azabicyclo[1.1.0]butanes under flash vacuum thermolysis (FVT) conditions was studied. It has been found that the thermal rearrangement of title compounds produces unstable 2‐aza‐1,3‐dienes. The formation of these products was established by reduction, by Diels−Alder reactions and by UV photoelectron spectroscopy. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

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Synthesis and Chemistry of Substituted 1-Azabicyclo[1.1.0]butanes

Cited by 46 publications

References 0 publications

Valence Isomerization of 2‐Phosphabicyclo[1.1.0]butanes

Valence Isomerization of 2‐Phosphabicyclo[1.1.0]butanes

Synthesis of New Quinolone Antibiotics Utilizing Azetidine Derivatives Obtained from 1-Azabicyclo[1.1.0]butane

Flash Vacuum Thermolysis of 1‐Azabicyclo[1.1.0]butanes. Photoelectron Spectrum of 3‐Phenyl‐2‐azabuta‐1,3‐diene

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