An enantioselective route to the pyrrolizidine ring system has been developed which uses an N-acyl anion cyclisation reaction as the key step. This methodology has provided the natural pyrrolizidines (−)-(1R, 8S)-1-hydroxy-pyrrolizidine 7, (−)-pyrrolizidin-1-ene-3-one 9 and (±)-trachelanthamidine 14. Extension of the process to an N-propionyl substrate provides ready access to a series of 2-methyl pyrrolizidines.

4-Benzyl-4-ethoxycarbonyl-1-substituted piperidines 1 (R(1) = PhCH(2), PhCO; R(2) = PhCH(2)) cyclise with polyphosphoric acid (PPA) to give spiro [indane-2,4'-piperidin]-1-ones 3 (R = PhCH,, PhCO), while 2-benzyl-2-ethoxycarbonyl-1-methylpiperidine 4 gives the N-methylspiro [indane-2,2'-piperidin]-1-one 5. 3,4,4a, 5-Tetrahydrobenz[g]isoquinolin-10(2H)-one 8 arises from PPA treatment of 1-benzoyl-4-benzyl-5-ethoxycarbonyl-1,2,3,4-tetrahydropyridine 7 (R = PhCO) while o-chloranil converts 1-benzoyl-4-benzyl-4-ethoxycarbonyl 1,4-dihydropyridine 6 (R = PhCO) into 4-benzyl-3-ethoxycarbonylpyridine 9. Phenyl(tribromomethyl)mercury reacts with 1-benzoyl-4-benzyl-4-ethoxycarbonyl-1,4-dihydropyridine 2 (R(1) = PhCO, R(2) = PhCH(2)) yielding 2-benzoyl-5-benzyl-7,7-dibromo-5-ethoxycarbonyl-2-azabicyclo[4.1.0] hept-3-ene 11, and with 1-benzoyl-4-benzyl-3-ethoxycarbonyl-1,4-dihydropyridine 6 (R = PhCO) to give 2-benzoyl-5-benzyl-7,7-dibromo-4-ethoxycarbonyl-2-azabicyclo[4.1.0]hept-3-ene 12, The structure of the latter is confirmed by X-ray crystallographic analysis. Catalytic hydrogenation of 2-benzoyl-5-benzyl-7,7-dichloro-5-ethoxyca [4,1,0]hept-3-ene 16 yields 2-benzoyl-5-benzyl-7,7-dichloro-4-ethoxycarbonyl-2-azabicyclo [4,1,0]heptane 21 which cyclises with PPA to give the tetracyclic product 22 in good yield, When 2-benzoy-5-benzyl-7,7-dichloro-4-ethoxycarbonyl azabicyclo[4.1.0] hept-3-ene 17 is hydrogenated it yields mainly 2-benzoyl-5-benzyl-7,7-dichloro-4-ethoxycarbonyl-2-azabicyclo[4. 1.0]heptane 25 but the dibromo analogue 12 under the same conditions gives two components thought to be 2-benzoyl-5-benzyl-7-endo-bromo-4-ethoxycarbonyl-2- azabicyclo [4.1.0]hept-3-ene 24 and 2-benzoy-5-benzyl-7-exo-bromo-4-ethoxycarbonyl-2-azabicyclo[4,1,0] hept-3-ene 23.

A new species ofLobelia (Campanulaceae: Lobelioideae) is described from Isla de Mona, a Caribbean island not previously known to harbor the genus. The small woody rosette-plants were collected in 1988 and 1992 at the northeastern corner of the island, where they grew from crevices in the vertical limestone cliffs, approximately 60 m above the sea. The new species,Lobelia vivaldii, belongs to sect.Tylomium, a group of approximately 36 suffruticose and woody species endemic to the Caribbean basin. Within that section, it is most similar to and apparently derived fromL. cirsiifolia, a less woody rain forest species found at higher elevations on several islands in the Lesser Antilles.

2-Chloro-N-tosylprop-2-enylamine (5; R = H) was converted into methyl 3-[N-(2-chloroprop-2-enyl)-N-tosylamino]propanoate (5; R = CH2CH2CO2Me) and into 3-[N-(2-chloroprop-2-enyl)-N-tosyl-amino]propanonitrile (5; R = CH2CH2CN). These, in turn, were converted into 4-[N-(2-chloroprop-2-enyl)-N-tosylamino]-1-methylbutan-2-ol [5; R = CH2CH2C(OH)Me2], 3-[N-(2-chloroprop-2-enyl)-N-tosylamino]-1-phenylpropan-1-one (5; R = CH2CH2COPh), 4-[N-(2-chloroprop-2-enyl)-N-tosylamino]-2-phenylbutan-2-ol [5; R = CH2CH2C(OH)(Me)Ph], 3-[N-(2-chloroprop-2-enyl)-N-tosylamino]-1-phenylpropan-1-ol [5; R = CH2CH2CH(OH)Ph], 4-[N-(2-chloroprop-2-enyl)-N-tosylamino]butan-2-ol [5; R = CH2CH2CH(OH)Me] and 3-[N-(2-chloroprop-2-enyl)-N-tosylamino]propanoic acid (5; R = CH2CH2CO2H). The alcohols [5; R = CH2CH2C(OH)Me2] and [5; R = CH2CH2CH(OH)Ph] were cyclised by 90% sulfuric acid to 5,5-dimethyl-N-tosylazepan-3-one (6; R1= R2= Me) and 5-phenyl-N-tosylazepan-3-one (6; R1= Ph, R2= H), respectively. 6,6-Dichloro-N-tosylazepan-4-one 7 was obtained from 3-[N-(2-chloroprop-2-enyl)-N-tosylamino]propanoic acid (5; R = CH2CH2CO2H)via the acid chloride and was further converted into 6-chloro-1,2,3,7-tetrahydro-N-tosylazepin-4-one (8, R = Cl) and into the 6-methoxy analogue (8; R = OMe).

Antibodies have been raised to a 1-benzazepine hapten and the properties of two of the strongly binding clones, designated C3 and C5, as catalysts examined. Neither antibody catalysed the reaction for which they were first generated, electrophilic substitution in the benzene ring, but C3 catalysed the hydrolysis of an aralkyl 4-nitrophenyl ester with a rate enhancement of more than 10(6) compared with the background solvolysis rate. The mechanism of the hydrolysis reaction is suggested to involve general base catalysis on the basis of chemical modification experiments and isotope effects on the reaction rate in D2O. The possibility that C3 might catalyse other reactions (elimination, deuterium exchange, and epoxide opening) was investigated but no other reactions were observed. In contrast, C5 catalysed none of the reactions investigated. The properties of the two antibodies are discussed with respect to their ability to bind compounds structurally related to the hapten.

ChemInformVolume 21, Issue 35 Heterocyclic Compounds ChemInform Abstract: Synthesis of the Imidazo(4,5-b)azepine Ring System. D. MACLEOD, D. MACLEOD Dep. Pure Appl. Chem., Univ. Strathclyde, Glasgow G1 1XL, UKSearch for more papers by this authorG. R. PROCTOR, G. R. PROCTOR Dep. Pure Appl. Chem., Univ. Strathclyde, Glasgow G1 1XL, UKSearch for more papers by this author D. MACLEOD, D. MACLEOD Dep. Pure Appl. Chem., Univ. Strathclyde, Glasgow G1 1XL, UKSearch for more papers by this authorG. R. PROCTOR, G. R. PROCTOR Dep. Pure Appl. Chem., Univ. Strathclyde, Glasgow G1 1XL, UKSearch for more papers by this author First published: August 28, 1990 https://doi.org/10.1002/chin.199035210AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinkedInRedditWechat No abstract is available for this article. References D. MACLEOD, G. R. PROCTOR, Synthesis of the Imidazo(4,5-b)azepine Ring System., J. Chem. Res., Synop., 1990, 88–89. Web of Science®Google Scholar Volume21, Issue35August 28, 1990 ReferencesRelatedInformation

AbstractRing expansion of the tetralone derivative (I) is only achieved with the carboxylate (I), giving the benzocyclooctene (III) in poor yield.

ChemInformVolume 20, Issue 19 Isocyclic Compounds ChemInform Abstract: Some Aspects of the Chemistry of Benzosuberone: Novel Synthesis of the 5,9-Methano-5H-benzocycloheptene and 6,9-Ethano-5H-benzocycloheptene Ring Systems. M. T. OMAR, M. T. OMAR Dep. Pure Appl. Chem., Univ. Strathclyde, Glasgow G1 1XL, UKSearch for more papers by this authorG. R. PROCTOR, G. R. PROCTOR Dep. Pure Appl. Chem., Univ. Strathclyde, Glasgow G1 1XL, UKSearch for more papers by this authorD. I. C. SCOPES, D. I. C. SCOPES Dep. Pure Appl. Chem., Univ. Strathclyde, Glasgow G1 1XL, UKSearch for more papers by this author M. T. OMAR, M. T. OMAR Dep. Pure Appl. Chem., Univ. Strathclyde, Glasgow G1 1XL, UKSearch for more papers by this authorG. R. PROCTOR, G. R. PROCTOR Dep. Pure Appl. Chem., Univ. Strathclyde, Glasgow G1 1XL, UKSearch for more papers by this authorD. I. C. SCOPES, D. I. C. SCOPES Dep. Pure Appl. Chem., Univ. Strathclyde, Glasgow G1 1XL, UKSearch for more papers by this author First published: May 9, 1989 https://doi.org/10.1002/chin.198919169Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinkedInRedditWechat No abstract is available for this article. References M. T. OMAR, G. R. PROCTOR, D. I. C. SCOPES, Some Aspects of the Chemistry of Benzosuberone: Novel Synthesis of the 5,9-Methano-5H-benzocycloheptene and 6,9-Ethano-5H-benzocycloheptene Ring Systems., J. Chem. Res., Synop., 1988, 383. Google Scholar Volume20, Issue19May 9, 1989 ReferencesRelatedInformation

La synthese des composes du titre est effectuee via la methyl-5 tetrahydro-6,7,8,9 benzocycloheptenone-6 qui est obtenue par agrandissement de cycle

α-Tetralones end an N-tosyl-tetrahydroquinol-4-one undergo 1-carbon ring-expansion on being subjected to the Wittig reaction followed by Prévost reaction (AgNO3/I2/MeOH).

Various N-(chloroprop-2-enyl)-, N-(3-chlorobut-2-enyl)-, and N-(4-chloropent-3- and -4-enyl)-proline derivatives, -succinimides, and -phthalimides have been synthesised and subjected to Lewis acid treatment. The following gave fruitful results: N-(4-chloropent-3-enyl)-5-hydroxy-2-pyrrolidone (25) gave 1-acetyl-1,2,3,6,7,7a-hexahydropyrrolizin-5-one (28); N-(4-chloropent-3-enyl)-3-hydroxy-2,3-dihydro-1H-isoindol-1-one (30) gave 1-endo-acetyl-1,2,3,9b-tetrahydropyrrolo[2,1-a] isoindol-5-one (31) which was isomerised to the exo-isomer; N-(4-chloropent-3-enyl)-3-methylene-2,3-dihydro-1H-isoindol-1-one (34) and N-(4-chloropent-3-enyl)-3-hydroxy-3-methyl-2,3-dihydro-1H-isoindol-1-one (33) gave 1-endo-acetyl-9b-methyl-1,2,3,9b-tetrahydropyrrolo[2,1-a]isoindol-5-one(35); N-[-2-(3,4-dimethoxyphenyl)ethyl]proline (42) gave 8,9-dimethoxy-1,2,3,5,6,10b-hexahydropyrrolo[2,1-a]isoquinoline (43), N-(2-chloroprop-2-enyl)-2-(2-hydroxy-2-propyl)pyrrolidine (44) gave 6-chloro-8,8-dimethyl-1,2,3,5,8,8a-hexahydroindolizine (47) and 8,8-dimethyl-1,2,3,7,8,8a-hexahydroindolizin-6(5H)-one (48) which were reduced to the corresponding alcohols; N-(4-chloropent-4-enyl)-3-hydroxy-2,3-dihydro-1H-isoindol-1-one (50) gave 7,8,11,11a-hexahydro-5H-azepino[2,1-a]isoindole-5,10(9H)-dione (51).

Summary Recent research by the authors on West Indian pteridophytes has made it possible to identify for the first time or to correct prior misidentifications of many illustrations of ferns and a few fern-allies from Hispaniola and Martinique which were published by Plumier in his Trait6 des Fougeres de l'Amerique. Many of these plates serve as types for species published by Linnaeus and other early authors, and so their identity is of considerable nomenclatural importance. The fern plates published by Plumier (1705) are remarkable for their accuracy, considering their age. Fee (1866, pp. 137-149) published the first identifications of these plates. Later both Jenman (1888) and Urban (1925) published their own identifications, and often we agree with one or both of their ascriptions. Even so, a number of the plates have been misidentified or have not been identified at all until now. We have been able to correct some of the earlier ascriptions and to update some of the outdated names that were used, as well as to identify some of the plates for the first time-which warrants publication of the following complete list. Now only t. 35, 50C, 102B, 133 and 161 remain unidentified, and t. 42, 59, and 153 are uncertain. For most of the plates, cross references from Plumier (1705) to his earlier Description des Plantes de l'Amerique (1693) can be found in Urban (1925, pp. 394-397); therefore, we cite only the page and plate in the Trait ..