Electronic spectra of 12-S-CIS conformationally locked retinals

The electronic absorption spectra of the four new 12-$\text{s}$-$\text{cis}$-locked retinals (1a–1d) bearing 7-$\text{trans}$, 11-$\text{trans}$ double bond geometries are described and compared with those of analogous 7-$\text{trans}$, 11-$\text{cis}$-geometries (1e–1h) and parent retinals (2a-h).     

o-quinone methides 2. Stereoselectivity in cycloaddition reactions of o-quinone methides with vinyl ethers

Cycloaddition reactions between vinyl ethers 3 and $\text{o}$-quinone methides 2, thermally generated from 2-hydroxybenzyl alcohols 1, have been studied. The structure and conformational preferences of the 4-substituted 2-ethoxy-(2,3)-dihydro-2$\text{H}$-benzopyrans 4–9 obtained, which show new interesting features, are discussed together with competitive kinetic data. The cycloaddition process is concerted and involves $\text{o}$-quinone methides in the $\text{E}$-configuration. The OEt-$\text{endo}$ transition state seems to be preferred with ethyl vinyl ether and $\text{Z}$-1-propenyl ethyl ether, whereas with $\text{E}$-1-propenyl ethyl ether the stereoselectivity of the cycloaddition process depends on substituents on the methylene group of the starting alcohol 1. These results are discussed in terms of $\text{endo}$ and $\text{exo}$ preference of the propenyl ether methyl group.     

The unexpected intramolecular C-arylation of 2-0-benzylated cyclic sugar derivatives: a useful 1,2-cis-C-glycosylation reaction

Upon treatment with tin(IV) chloride, perbenzylated glycofuranosyl acetates such as 3 or 6 undergo an unusual, intramolecular α-$\text{C}$-arylation resulting from the internal Friedel-Crafts alkylation of the 2-$\text{O}$-benzyl substituent.     

Biosynthetic pathway of iridoid glucosides in Gardenia jasminoides f. grandiflora cell suspension cultures after iridodial cation formation

Administration of ²H- or ¹³C-labeled monoterpenes to $\text{Gardenia}$$\text{jasminoides}$ f. $\text{grandiflora}$ cell suspension cultures demonstrated that iridoid glucosides of the suspension cultures are biosynthesized, after iridodial cation formation from 10-oxocitral (3), via 8-epiiridodial (13), 8-epiiridotrial (14), boschnaloside (8-epiiridotrial glucoside) (12) and dehydroiridotrial glucoside (8). In addition, the coexistence of a route via iridodial cation (4), dehydroiridodial (6), dehydroiridotrial (15) and dehydroiridotrial glucoside (8) is conceivable.     

A synthetic approach to (+)-aldosterone and its relatives (2)- a stereoselective synthesis of (+)-trans-4,5-(4-methoxybenzo)- 1β , 7aβ - ( 2α-methoxymethyl- 5 -oxofuro) hydrindane

A stereoselectivity in an intramolecular cycloaddition of the olefinic $\text{o}$-quinodimethanes 13 and 23 generated $\text{in}$$\text{situ}$ from the thermolysis of optically active 4β-[2-(4-methoxybenzocyclobutenyl)ethyl] -5α-methoxymethyl-3-phenyl-thio-methylenefuran-2-ones 12 and 22, respectively, is studied and a stereoselective synthesis of (+)-$\text{trans}$-4,5-( 4-methoxybenzo) -1β,7aβ-(2α-methoxymethyl-5-oxofuro)hydrindane 1 is also described.     

Isolation and structure determination of nigellicine,a novel alkaloid from the seeds of nigellasativa

The structure of nigellicine (1) , an unusual alkaloid from the seeds of $\text{Nigella}$$\text{sativa}$, was determined by x-ray diffraction and spectroscopic techniques.     

The first x-ray structure determination of a z-phosphaethylene: z-2-phenyl-1-(2,4,6-tri-t-butylphenyl)phosphaethylene

The sterically protected $\text{Z}$-phosphaethylene, $\text{Z}$-2-phenyl-1-(2,4,6-tri-t-butylphenyl)phosphaethylene (1-Z), was analyzed by X-ray crystallography.     

A facile transformation of bicyclic keto esters to bisprotected (±)-8-epithienamycin via enol activation

A facile “one-pot” transformation of bicyclic keto ester (2) to bisprotected (±)-8-epithienamycin $\text{via}$ enol phosphate activation followed by the addition-elimination reaction of $\text{N}$-protected cysteamine derivative is described.     

Optically active 2-p-tolylsulfinylacrylate a novel chiral dienophile which exhibits high reactivity and diastereoselectivity

The Diels-Alder reaction of a novel chiral dienophile, alkyl ($\text{S}$)-2-$\text{p}$-tolylsulfinylacrylates 1 with anthracene and cyclopentadiene showed high diastereoselectivity under the chelation controlled condition.     

Substituent influence on the indolization with pcl3 of some o,m,p-substituted phenylhydrazones

The indolization of deoxybenzoin $\text{o}$,$\text{m}$,$\text{p}$ (Me, MeO, Cl), $\text{p}$-NO₂ and $\text{m}$-EtO-phenylhydrazones (1) by the above reaction has been examined. All the reactions are carried out at room temperature and high yields of the corresponding indoles (2) are obtained even when -NO₂ substituent is present. In this case longer reaction time is necessary. Alkoxyphenylhydrazones give the corresponding indoles (2) in high yields without showing collateral reactions which indeed are present in several Fischer routes on these derivatives. $\text{m}$-Substituted phenylhydrazones (1) give a mixture of 4- and 6-substituted indoles in which the 6-isomer is always prevalent, a feature not inherent in the Fischer reactions. The regioselectivity is enhanced by the substituent steric hindrance increasing. The reaction can be also carried out at 0°C with a further improvement of its regioselectivity.     

Transfer to monomer in the polymerization of N-(3-dimethylaminophenyl) maleimide and N-(3-dimethylamino-6-methylphenyl) maleimide

The kinetics of the homopolymerizations of styrene, N-(3-dimethylaminophenyl) maleimide (I) and N-(3-dimethylamino-6-methylphenyl) maleimide (II) in benzene and dimethylformamide, and the molecular weights of the polymers were studied. N-(3-Dimethylaminophenyl) succinimide, regarded as a model for polymer I, did not affect the polymerization of styrene. The data indicate degradative transfer of polymer radicals to dimethylformamide and pronounced transfer to monomers I and II (C_M ≈ 0.06–0.07). The value of $\text{k}{}_{\mathrm{p}}\text{/k}{}_{\mathrm{t}}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ for II is 0.09 $\text{dm}{}^{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$$\text{mole}{}^{\mathrm{<mtext>?</mtext><mtext>1</mtext><mtext>2</mtext>}}$$\text{s}{}^{\mathrm{<mtext>?</mtext><mtext>1</mtext><mtext>2</mtext>}}$.     

The convenient route to cd fragment for the synthesis of vitamin D3 relatives

The efficient degradation of $\text{1}$ to the α-methylene ketone $\text{4}$ is described. Compound $\text{4}$ was then converted to the allylic alcohol $\text{8a}$ - the precursor of vitamin D³ relatives.     

Untersuchungen an stoffwechselprodukten von mikroorganismen,-XXII1: Untersuchung der pigmente aus flavobacterium spec. stamm C12

The pigment complex from Flavobacterium spec strain C$\text{1}\text{2}$ consists of pigments 1a to 1d whose isolation and structure elucidations are reported. These pigments exclusively belong to the new class of flexirubin type pigments. Up to now, pigments of this type have been found in gliding bacteria only.     

Syncarpurea,a novel metabolite from uvaria afzelii

The isolation and structure determination of syncarpurea (1), a novel urea from $\text{Uvaria afzelii}$ is reported.     

13C NMR of carbonyl compounds. 3. Structure and dynamics of protonated enones and dienones

The unsaturated ketones $\text{1}$1 – $\text{10}$10 were protonated at low temperatures and studied by dynamic ¹³C NMR spectroscopy. Four interconverting stereoisomers were detected which differ in their conformation with respect to the CO and CC (enone) single bond.     

The structure of tatsinine,a novel c19-diterpenoid alkaloid from delphinium tatsienense franch

A novel C₁₉-diterpenoid alkaloid designated as tatsinine has been isolated from the roots of $\text{Delphinium}$$\text{tataienence}$ and its structure (3) has been derived from ¹H NMR and ¹³C NMR spectroscopic evidence.     

Completely stereoselective synthesis of all four stereoisomeric 1-carbamoyloxy-1,3-alkadienes via anti-diastereoselective homoaldol reaction from aldehydes and a single carbon-three-unit

Lithiation of both ($\text{Z}$)- and ($\text{E}$)-3-trimethylsilyl-2-propenyl $\text{N}$,$\text{N}$-diisopropyl carbamate 2 affords the (2$\text{E}$) -lithium compound 3. Aluminium- or titanium-mediated addition to aldehydes, 4 gives (1$\text{E}$)-(3$\text{R}$*4$\text{S}$*)-enol carbamates 7. A stereospecific Peterson elimination (borontriflouride- or base-mediated) introduces the second double bond either with (3$\text{E}$)- or with (3$\text{Z}$)-configuration. So just by reagent selection for each of the two steps, (1$\text{E}$,3$\text{E}$)-, (1$\text{E}$,3$\text{Z}$)-, (1$\text{Z}$,3$\text{E}$)-, or (1$\text{Z}$,3$\text{Z}$)- dienes 8 - 11, respectively, are prepared with stereoselectivities up to > 99.7%     

Nucleosides-126: Selective methylation of the C-nucleoside, ψ-isocytidine and its 2$́-deoxy analog. Synthesis of 1-methyl, 3-methyl and 4-o-methyl derivatives

Methods were developed to prepare 1 -methyl-, 3-methyl- and 4-0-methyl-ψ-isocytidine by selective methylation.3$\text{,}\text{?}$5$\text{-}\text{?}$O-Tetraisopropyldisiloxanyl-ψ isocytidine (8) was trimethylsilylated and then treated with MeI and, after deprotection, 1 -methyl-ψ isocytidine (6) was obtained. The 2$\text{-}\text{?}$deoxy analog (7) was also prepared in a similar manner from the 2$\text{-}\text{?}$deoxy analog (10) of 8. Treatment of 8 with CH₂N₂ afforded the 3-methyl-ψ-isocytidine derivative (19) as the major product. Methylation with diazomethane also occurred mainly on N3 of the 2$\text{-}\text{?}$deoxy analog 10 to form 20. Removal of the 3$\text{,}\text{?}$ 5$\text{-}\text{?}$O-protecting group from 19 and 20 afforded 3-methyl-ψ-isocytidine (14) and its 2-deoxy analog (15), respectively. 2-N-Acetyl- 3$\text{,}\text{?}$5$\text{-}\text{?}$O-tetraisopropyldisiloxanyl-ψ-isocytidine (24), on the other hand, gave the 4-O-methyl derivative (25) as the major product upon CH₂N₂ treatment. Subsequent deprotection of 25 afforded 4-O-methyl-ψ-isocytidine (29). aiv51b1p33b     

A stereoselective total synthesis of Δ9-progesterone via an intramolecular cycloaddition reaction

A stereoselective total synthesis of 19-nor-Δ⁹⁽¹⁰⁾-progesterone (14) was achieved through des-A B-aromatic steroid (3) which was obtained by an intramolecular cycloaddition of the $\text{o}$-quinodimethane generated $\text{in situ}$ from the thermolysis of 3-isopropenyl-5-(4-metho-xybenzocyclobutenyl)pentan-2-one-2-ethylene ketal (2), and the compound (14) thus obtained was further converted into Δ⁹-progesterone (18).     

The structure of dehydrated Na zeolite A (SiAl = 1.09) by neutron profile refinement

Contrary to the recent work of J. M. Thomas et al. (J. Chem. Soc. Chem. Commun., 678, 1981), it was found that a high-resolution neutron powder diffraction pattern of a sample of dehydrated Na zeolite A (with $\text{Si}\text{Al}$ ratio 1.09) can be indexed and refined in the cubic groups $\text{Pm}\text{3}\text{m (R}{}_{\mathrm{<mtext>pw</mtext>}}\text{= 11.0\%)}$ (A. K. Cheetham and J. C. Taylor, J. Solid State Chem.21, 253, 1977) and $\text{Fm}\text{3}\text{c (R}{}_{\mathrm{<mtext>pw</mtext>}}\text{= 10.3\%)}$, whereas in the rhombohedral space group $\text{R}\text{3}$ refinement was unsuccessful. For two other samples having $\text{Si}\text{Al}$ ratios of 1.03 and 1.12 the diffraction patterns again showed no evidence of rhombohedral distortion and can be indexed using a cubic unit cell. It appears that the Si, Al ordering of zeolite A, and hence the crystal symmetry, must depend upon the conditions of preparation of the zeolite.