bluuebunny/crossref_metadata_2025_split huggingface dataset:
High‐Yield Syntheses of Sodium, Potassium, and Thallium Hydrotris[3,5‐bis(trifluoromethyl)pyrazolyl]borates and the X‐ray crystal structure of {hydrotris[3,5‐bis(trifluoromethyl)pyrazolyl]borato} thallium(I)
Authors: Renn Oliver , Venanzi Luigi M. , Marteletti Arianna , Gramlich Volker 
Published: December 2004

AbstractAn improved synthesis of 3,5‐bis(trifluoromethyl)pyrazole (1) is described. This compound was used for the high‐yield syntheses of the tris(pyrazoly1)borates Nd[HB(3,5‐(CF3),‐pz)3] (2a) and the corresponding potassium salt, 2b, starting from 1 and NaBH4 and KBH4, respectively. A convenient route to the corresponding thallium(I) salt, 2c, using thallium(I) acetate and either 2a or 2b in CHCI3, is also described. The sodium (3a), potassium (3b), and thallium (3c) salts of bis(pyrazolyl)borate [H2B(3,5‐(CF3)2‐pz)2]− were also prepared. The above pyrazolylborates were characterized by 1H‐, 13C‐, 19F‐, and 11B‐NMR spectroscopy. The X‐ray crystal structure of the thallium derivative 2c was determined. The compound crystallizes in the monoclinic space group P21/m with a = 8.248(9) Å, b = 15.034(12) Å c = 9.243(8) Å, β = 100.10(7)°, Z = 2. The Tl‐atom adopts a pyramidal geometry with respect to the three N‐atoms. However, two TI–N distances (2.725(7) Å) are longer than the third (2.675(10) Å).
Diastereoselective Radical Reactions Starting from Cyclic Iodohydrin Derivatives
Authors: Moufid Nadira , Renaud Philippe 
Published: December 2004

AbstractThe stereoselectivity of radical reactions using cyclic iodohydrins and 2‐alkoxy iodides was investigated on a simple model system obtained from indene (see 1a−d). The low level of stereoselectivity inherent to this type of systems could neither be overcome by using large protective group on the O‐atom of 1c nor by complexation with Lewis acids. However, starting from the free alcohol 1c, it was possible to obtain very high selectivities (trans/cis > 100:1) by forming an aluminium alkoxide derivative upon treatment with methylaluminium bis[2,6‐di(tert‐butyl)‐4‐methylphenoxide] (MAD) before running the radical reaction. Despite the high steric demand of these complexes, the reactions gave satisfactory yields even for the formation of CC bonds.
Glycosylidene Carbenes. Part 21. Synthesis of N‐tosylglycono‐1,4‐lactone hydrazones as precursors of glycofuranosylidene carbenes
Authors: Mangholz Sissi E. , Vasella Andrea 
Published: December 2004

AbstractThe N′‐(glycofuranosylidene)toluene‐4‐sulfonohydrazides 5 and 10 (Scheme 1) were prepared in good yields by oxidation (1,3‐dibromo‐5,5‐dimethylhydantoin/Et3N) of the N′‐glycosyltoluene‐4‐sulfonohydrazides 4 and 9, which were obtained from 2,3,5‐tri‐O‐benzyl‐D‐ribose (3) and 2,3,5‐tri‐O‐benzyl‐D‐arabinose (8), respectively, and toluene‐4‐sulfonohydrazide. The analogous naphthalene‐2‐sulfonohydrazides 7 and 12 were similarly prepared from 3 and 8 via 6 and 11. Photolysis in the presence of phenol of the sodium salt 15 (Scheme 2), best generated in situ, yielded the anomeric glycosides 16, some 5, and traces of the glycosides (1R)/(1S)‐17. Photolysis of 15 in THF gave the sulfones α‐D/β‐D‐18. Photolysis of 15 (quartz filter) and dimethyl fumarate led to a single cyclopropane 19, the sulfones α‐D/β‐D‐18, and the N‐(ribofuranosyl)‐N′‐(ribofuranosylidene)toluene‐4‐sulfonohydrazide 20. Similarly, N‐phenylmaleimide afforded the cyclopropanes 21 and 22. Photolysis of the sodium salt of 10 and phenol afforded the anomeric glycosides α‐D/β‐D‐23, the C‐glycoside 24, and the sulfone 25. Photolytic glycosidation of 15 with N6‐benzyladenine gave the two nucleosides 26 and 27 (Scheme 3).
(±)‐4‐Amino‐4,5‐dideoxyribose, (±)‐4‐amino‐4‐deoxyerythrose, and (±)‐dihydroxyproline derivatives from N‐dienyl‐γ‐lactams
Authors: Behr Jean‐Bernard , Defoin Albert , Mahmood Naheed , Streith Jacques 
Published: December 2004

AbstractHetero‐Diels‐Alder cycloaddition of acylnitroso dienophile 4 with the N‐(butadienyl)pyrrolidinone derivatives 2a, b led with complete regioselectivity to the oxazine adducts 5a, b (Scheme 1). Sequential osmylation, protection of the ensuing glycol, and reduction of the NO bond gave the expected hemiaminals 11a, b which were characterized by their crystalline sulfite adducts 12a, b (Schemes 1 and 2). Deprotection and saponification of the latter led to aminodeoxyerythrose and to aminodeoxyribose derivatives as an equilibrium of pyrrolidinose equivalents, i.e., hemiaminals 14a, b, imines 14′a, b, and dimers 14″a,b, respectively (Scheme 3). Hydrocyanic acid addition to 11a, b led ultimately to the proline derivatives 16a, b (Scheme 2). Compound 11b proved to be an inhibitor of syncytium formation in AIDS‐infected cells.
Total Synthesis with a Chirogenic Opening Move Demonstrated on Steroids with Estrane or 18a‐Homoestrane Skeleton
Authors: Quinkert Gerhard , Del Grosso Michael , Döring Astrid , Döring Wolfgang , Schenkel Ralf I. , Bauch Markus , Dambacher Gernot T. , Bats Jan W. , Zimmermann Gottfried , Dürner Gerd 
Published: December 2004

AbstractA concept of first choice for the synthesis of the title compounds had been proposed by Dane in the late 1930s. It was soon turned down, because the opening move–a chirogenic Diels‐Alder reaction – did not work. With Lewis acids as mediators, however, a successful start has been achieved now. With Ti complexes of chelating ligands (Seebach's TADDOLs (= α,α,α′,α′‐tetraaryl‐1,3‐dioxolane‐4,5‐dimethanols)), enantioselective formation of the desired adducts does occur. Efficient total syntheses of 2 and 3a have been accomplished.
Bis‐allylic Reactivity of the Funicolides, 5,8(17)‐diunsaturated briarane diterpenes of the sea pen Funiculina quadrangularis from the tuscan archipelago, leading to 16‐nortaxane derivatives
Authors: Guerriero Antonio , D'Ambrosio Michele , Pietra Francesco 
Published: December 2004

AbstractFunicolides A–C (1–3), D (5), and E (7) and 7‐epifunicolide A (4), new 5,8(17)‐diunsaturated briarane diterpenes, as well as the known analogue brianthein W (6), were isolated from the pennatulacean coral Funiculina quadrangularis (PALLAS, 1766) collected in the Tuscan archipelago. Easy degradation under oxidative and/or basic conditions served to assign the ester groups at C(2) or C(14), while revealing bis‐allylic reactivity at C(7) with formation of 16‐nortaxane derivatives.
Caulerpenyne‐Amine Reacting System as a Model for in vivo Interactions of Ecotoxicologically Relevant Sesquiterpenoids of the mediterranean‐adapted tropical green seaweed caulerpa taxifolia
Authors: Guerriero Antonio , Depentori Daniela , D'Ambrosio Michele , Pietra Francesco 
Published: December 2004

AbstractCaulerpenyne (1), the most abundant of the ecotoxicologically relevant sesquiterpenoids of the Mediterranean‐adapted tropical green seaweed Caulerpa taxifolia, was found to react with Et3N or pyridine in MeOH by initial deprotection of C(1)HO to give oxytoxin 1 (2a), previously isolated from the sacoglossan mollusc Oxynoe olivacea. With BuNH2, without any precaution to exclude light, 1 gave the series of racemic 3 and 4, and achiral (4E,6E)‐5, (4E,6Z)‐5, (4Z,6E)‐5, and (4Z,6Z)‐5 pyrrole compounds, corresponding to formal C(4) substitution, 4,5‐β‐elimination, and (E/Z)‐isomerization at the C(4)C(5) and C(6)C(7) bonds. Changing to CDCl3 as solvent in the dark, 1 gave cleanly, via 2a as an intermediate, 3 and (4E,6E)‐5. The latter proved to be prone to (E/Z)‐photoisomerization. Under standard acetylation conditions, 3 gave (4E,6E)‐5 via acetamide 7 as an intermediate. Particular notice is warranted by selective deprotection of 1 at C(1), mimicking enzyme reactions, and unprecedented formation of pyrrole compounds from freely‐rotating, protected 1,4‐dialdehyde systems.
Nucleotides. Part XLV. Synthesis of new (2′–5′)adenylate trimers, containing 5′‐amino‐5′‐deoxyadenosine residues at the 5′‐end of the oligoadenylate chain, and of its analogues, carrying a 9‐[(2‐hydroxyethoxy)methyl]adenine residue at the 2′‐terminus
Authors: Kvasyuk Evgeny I. , Kulak Tamara I. , Mikhailopulo Igor A. , Charubala Ramamurthy , Pfleiderer Wolfgang 
Published: December 2004

AbstractThe 5′‐amino‐5′‐deoxy‐2′,3′‐O‐isopropylideneadenosine (4) was obtained in pure form from 2′,3′‐O‐isopropylideneadenosine (1), without isolation of intermediates 2 and 3. The 2‐(4‐nitrophenyl)ethoxycarbonyl group was used for protection of the NH2 functions of 4 (→7). The selective introduction of the palmitoyl (= hexadecanoyl) group into the 5′‐N‐position of 4 was achieved by its treatment with palmitoyl chloride in MeCN in the presence of Et3N (→5). The 3′‐O‐silyl derivatives 11 and 14 were isolated by column chromatography after treatment of the 2′,3′‐O‐deprotected compounds 8 and 9, respectively, with (tert‐butyl)dimethylsilyl chloride and 1H‐imidazole in pyridine. The corresponding phosphoramidites 16 and 17 were synthesized from nucleosides 11 and 14, respectively, and (cyanoethoxy)bis(diisopropylamino)phosphane in CH2Cl2. The trimeric (2′–5′)‐linked adenylates 25 and 26 having the 5′‐amino‐5′‐deoxyadenosine and 5′‐deoxy‐5′‐(palmitoylamino)adenosine residue, respectively, at the 5′‐end were prepared by the phosphoramidite method. Similarly, the corresponding 5′‐amino derivatives 27 and 28 carrying the 9‐[(2‐hydroxyethoxy)methyl]adenine residue at the 2′‐terminus, were obtained. The newly synthesized compounds were characterized by physical means. The synthesized trimers 25–28 were 3‐, 15‐, 25‐, and 34‐fold, respectively, more stable towards phosphodiesterase from Crotalus durissus than the trimer (2′–5′)ApApA.
Syntheses and Reactions of 1′,2′‐Unsaturated 2′,3′‐Seconucleoside Analogues
Authors: Vrček Valerije , Čaplar Vesna 
Published: December 2004

AbstractThe 1′,2′‐unsaturated 2′,3′‐secoadenosine and 2′,3′‐secouridine analogues were synthesized by the regioselective elimination of the corresponding 2′,3′‐ditosylates, 2 and 18, respectively, under basic conditions. The observed regioselectivity may be explained by the higher acidity and, hence, preferential elimination of the anomeric H–C(1′) in comparison to HC(4′). The retained (tol‐4‐yl)sulfonyloxy group at C(3′) of 3 allowed the preparation of the 3′‐azido, 3′‐chloro, and 3′‐hydroxy derivatives 5–7 by nucleophilic substitution. ZnBr2 in dry CH2Cl2 was found to be successful in the removal (85%) of the trityl group without any cleavage of the acid‐sensitive, ketene‐derived N,O‐ketal function. In the uridine series, base‐promoted regioselective elimination (→19), nucleophilic displacement of the tosyl group by azide (→20), and debenzylation of the protected N(3)‐imide function gave 1′,2′‐unsaturated 5′‐O‐trityl‐3′‐azido‐secouridine derivative 21. The same compound was also obtained by the elimination performed on 2,2′‐anhydro‐3′‐azido‐3′‐azido‐3′‐deoxy‐5′‐O‐2′,3′‐secouridine (22) that reacted with KO(t‐Bu) under opening of the oxazole ring and double‐bond formation at C(1′).
Synthesen, chemische Reaktionen und NMR‐spektroskopische Untersuchungen substituierter Phosphonopyruvate
Authors: Feistauer Helmut , Neidlein Richard 
Published: December 2004

Phosphonopyruvates: Syntheses, NMR Investigations, and ReactionsThe new 3‐(diethoxyphosphoryl)‐2‐oxopropanoates 5–24 and ‐propanamides 25–38 with various substituents at C(3) were prepared in moderate‐to‐good yields (Schemes 2 and 3, Tables 1 and 2). It was shown that they adopt a preferred conformation in which the diethoxyphosphoryl group and the substituent at C(4) are antiperiplanar to each other (see B). The keto‐enol tautomerization of phosphonopyruvates with PhC(3) (see 20) and MeSC(3) (see 24 and 33) was examined. In CHCl3, two tautomeric species exist, whereas in dimetylsulfoxide (DMSO), three tautomeric forms are observed. Oxime ethers, an oxime, and a phenylhydrazone of unsubstituted phosphonopyruvates were prepared (see 40–44), and quinoxalin‐2(1H)‐ones could be obtained from the reaction of pyruvates with 4,5‐dimethylbenzene‐1,2‐diamine (see 45–47).
On the Way to Glycoprocessing Inhibitors. Synthesis of an imidazo‐L‐xylo‐piperidinose derivative
Authors: Frankowski Andrzej , Deredas Dariusz , Nouen Didier Le , Tschamber Théophile , Streith Jacques 
Published: December 2004

AbstractAn eight‐step synthetic sequence led from the known D‐xylo‐pentodialdose 8 to imidazo‐L‐xylo‐piperidinose 15, the key steps being the build‐up of imidazole compound 12 by a van Leusen methodology and the intramolecular SN2 ring closure of the O‐triflated benzylidene derivative 13. xylo‐Piperidinose 15 appears in a half‐chair conformation like the oxocarbonium ions which are the postulated intermediates in the glycoprocessing of the pyranose polysaccharides. This bicyclic azasugar should be a glycosidase inhibitor.
Eine überraschende Ringerweiterung von 3‐(Dimethylamino)‐2,2‐dimethyl‐2H‐azirin zu 4,5‐Dihydropyridin‐2(3H)‐on‐Derivaten
Authors: Hugener Martin , Heimgartner Heinz 
Published: December 2004

An Unexpected Ring Enlargement of 3‐(Dimethylamino)‐2,2‐dimethyl‐2H‐azirine to 4,5‐Dihydropyridin‐2(3H)‐one DerivativesThe reaction of 3‐(dimethylamino)‐2,2‐dimethyl‐2H‐azirine (1a) and 4,4‐disubstituted 2‐(trifluoromethyl)‐1,3‐oxazol‐5(4H)‐ones 7 in MeCN at 70° afforded 5‐(dimethylamino)‐3,6‐dihydropyrazin‐2(1H)‐ones 10 (Scheme 4), whereas no reaction could be observed between 1a and 2‐allyl‐4‐phenyl‐2‐(trifluoromethyl)‐1,3‐oxazol‐5(2H)‐one (8a) or 4,4‐dibenzyl‐2‐phenyl‐1,3‐oxazol‐5(4H)‐one (9). The formation of 10 is rationalized by a mechanism via nucleophilic attack of 1a onto 7. The failure of a reaction with 9 shows that only activated 1,3‐oxazol‐5(4H)‐ones bearing electron‐withdrawing substituents do react as electrophiles with 1a. The amino‐azirine 1a and 2,4‐disubstituted 1,3‐oxazol‐5(4H)‐ones 2b–e in refluxing MeCN undergo a novel ring enlargement to 4,5‐dihydropyridin‐2(3H)‐ones 11 (Scheme 5). Several side products were observed in these reactions. Two different reaction mechanisms for the formation of 11 are proposed: either 1a undergoes a nucleophilic addition onto the open‐chain ketene tautomer of 2 (Scheme 6), or 2 reacts as CH‐acidic compound (Scheme 7).
3′,4′‐Diethynl‐2′,3′,5′‐trideoxy‐5′‐noruridine: A new self‐polymerizable 2′‐deoxyribonucleoside analogue
Authors: Amin Mahmoud Ahmed , Stoeckli‐Evans Helen , Gossauer Albert 
Published: December 2004

AbstractIn 10 steps, 3′,4′‐diethynyl‐2′,3′,5′‐trideoxy‐5′‐noruridine (14) was synthesized in 5% overall yield from commercial uridine, using conventional methods of nucleoside chemistry. As two functional groups capable to react with each other are present in the same molecule, the synthetic compound is able to form polymers, similar to the polynucleotides, by an acetylene coupling reaction.
Synthesis of Thiophene‐Substituted Spiropyrans and Spirooxazines, Precursors of Photochromic Polymers
Authors: Moustrou Corinne , Samat André , Guglielmetti Robert , Dubest Roger , Garnier Francis 
Published: December 2004

AbstractThe synthesis of spiropyrans 11 and 12 and spirooxazines 13–17 containing a thiophene moiety is described. Two different synthetic approaches were used. The spectrokinetic properties of these new compounds are reported.
Unparalleled, Enormous Metal–Carbon Bond Strength in PdCH2I+
Authors: Schwarz Joseph , Heinemann Christoph , Schröder Detlef , Schwarz Helmut , Hrušák Jan 
Published: December 2004

AbstractThermalized Pd+ cations activate methyl iodide by selective cleavage of a CH bond under formation of PdCH2I+ and an H‐atom. This finding implies that the interaction energy between the metal cation and the CH2I fragment and thus the metal–carbon bond strength exceeds 103 kcal/mol. Theory predicts that the energetically most favorable isomer of this ion exhibits the Pd+CH2I structure, which is stabilized by an unprecedented bridging interaction between the two heavy atoms Pd and I.
The Chemistry of Stable Carbenes. Part 2. Benzoin‐type condensations of formaldehyde catalyzed by stable carbenes
Authors: Henrique Teles J. , Melder Johann‐Peter , Ebel Klaus , Schneider Regina , Gehrer Eugen , Harder Wolfgang , Brode Stefan , Enders Dieter , Breuer Klaus , Raabe Gerhard 
Published: December 2004

AbstractStable carbenes derived from thiazole, 1H‐imidazole, and 4H‐1,2,4‐triazole are efficient catalysts for benzointype condensations of formaldehyde. Catalysts derived from N‐substituted thiazolium salts trimerize formaldehyde to dihydroxyacetone (II). Catalysts based on 1,4‐disubstituted 4H‐1,2,4‐triazol‐1‐ium salts give glycolaldehyde (I) as the main product and no II, whereas N,N′‐disubstituted 1H‐imidazol‐3‐ium salts yield mixtures of both products. The isolation of several intermediates in the catalytic cycle provide a better insight into the reaction mechanism.
Solvent‐shared radical ion pairs [pyrene·⊖Na⊕(C2H5)2]∞: ESR evidence for two different aggregates in solution, room temperature crystallization, and structural proof of another polymorphic modification
Authors: Näther Christian , Bock Hans , Claridge Rodney F. C. 
Published: December 2004

AbstractThe reduction of pyrene with sodium in aprotic diethyl ether allows to crystallize the extremely air‐sensitive radical ion pair pyrene‐sodium‐diethylether. The single‐crystal structure determination at 130 K shows that each sodium counter cation, solvated by one diethyl‐ether molecule, is η3‐ and η6‐coordinated to one of the short‐axis six‐membered rings of two pyrene radical anions. The resulting dibenzene‐sodium sandwiches form a string, in which the hydrocarbon planes are canted to each other by 62°. In the pyrene radical‐anion skeleton, no distortion due to its negative charge can be detected relative to that of the neutral molecule. From the temperature‐dependent signal multiplets of preceding ESR investigations, the solvent‐separated pyrene radical anion as well as two different contact radical‐ion pairs had been identified and their structures in solution approximated by potential‐energy estimates. Referring to the recently discovered long‐axis Na⊕ contact ion pair polymorph, crystallized at lower temperatures, the structure reported here represents the second and probably thermodynamically more stable one. Both the ESR and the structural results provide some insight into the multidimensional networks of equilibria in aprotic solution, which are activated by alkali‐metal reduction of unsaturated organic compounds.
Oligonucleotide Synthesis on Polystyrene‐Grafted Poly(tetrafluoroethylene) Support
Authors: Birch‐Hirschfeld Eckhard , Gührs Karl‐Heinz , Földes‐Papp Zeno , Seliger Hartmut 
Published: December 2004

AbstractSupports consisting of a thin layer (2–10%) of polystyrene (PS) grafted onto a poly(tetrafluoroethylene) (PTFE) core are an interesting alternative to controlled pore glass (CPG) carriers in oligonucleotide synthesis. The beads are mechanically stable, do not show significant swelling, and allow effective removal of substrates by short washing steps with organic solvents. PTFE‐PS as an organic polymer has generally more hydrophobic properties than inorganic polymer supports and, therefore, is well compatible with organic solvents such as anhydrous MeCN. We found PTFE with a content of 2–3% PS graft to be a very good support for the synthesis of oligonucleotides of extended length. In comparison, PTFE with 5–10% grafted PS is especially useful for large‐scale syntheses. Functionalization procedures minimized in the extent of side reactions are described as well as examples for the use of the supports in syntheses of oligonucleotides both on large scale and of extended chain length.
Synthese von ‘Push‐Pull’‐ Eninen
Authors: Berger Daniel , Bartlome Andreas , Neuenschwander Markus 
Published: December 2004

Synthesis of ‘Push‐Pull’ Enynes‘Push‐pull’ enynes 1a–1f are easily available by Pd catalyzed coupling of stannyl‐ynamines 15 and silylynamines 16 with β‐iodo‐enones 8 (Schemes 7 and 8).
Metal Complexes with Macrocyclic Ligands. Part XLI. Nickel(II) and copper(II) complexes with mono‐N‐functionalized dithiadiazamacrocycles
Authors: Hörmann Esther , Riesen Pascale C. , Neuburger Markus , Zehnder Margareta , Kaden Thomas A. 
Published: December 2004

AbstractThree N2S2 macrocycles (3, 10, 12) carrying an amino group as a pendant arm have been synthesized and their complexation properties towards Ni2+ and Cu2+ studied. The crystal structures of the Cu2+ complexes with 10‐methyl‐1,4‐dithia‐7,10‐diazacyclododecane‐7‐ethanamine (3) and 11‐methyl‐1,4‐dithia‐8,11‐diazacyclotetradecane‐8‐ethanamine (10) show that, in both cases, the Cu2+ is pentacoordinated by the four donor atoms of the macrocycle and the amino group of the side chain. In aqueous solution, however, two forms of the complexes with stoichiometries [MLH] and [ML] (M = Cu2+ or Ni2+) have been observed. In [MLH], the amino group is protonated and does not bind to the metal ion, whereas in [ML] the amino group is bound, and a pentacoordinated geometry results. The pKa values for the equilibrium [ML] + H+⇌[MLH]+ decrease in the order 12 > 10 > 3, indicating that the 2‐aminoethyl side chain binds better to the Cu2+ than the 3‐aminopropyl side chain. Cyclic voltammetry for the Cu2+/Cu+ pair shows that the 2‐aminoethyl pendant arm stabilizes the Cu2+ oxidation state, when the metal ion is in the 14‐membered ring (10), whereas it stabilizes Cu+ for the 12‐membered macrocycle (3).
Oligosaccharide Analogues of Polysaccharides. Part 6. Orthogonal protecting/activating groups in an improved binomial synthesis of ‘acetyleno‐oligosaccharides’
Authors: Cai Chengzhi , Vasella Andrea 
Published: December 2004

AbstractBromination of the monosilylated dialkynylated monomer 1a (Scheme 1), dimer 3 and tetramer 5 by N‐bromosuccinimide (NBS) in the presence of CF3COOAg gave 2, 4, and 6, respectively, in over 93%. Similar conditions led to bromodesilylation. Either silyl group of the diprotected monomer 1c was selectively removed by bromolysis. On the one hand, bromodesilylation of 1c gave 2 in yields varying between 80 and 99%. On the other hand, bromodesilylation of 7, obtained from 1c by hydrolytic removal of the tetrahydro‐2H‐pyran‐2‐yl (Thp) group, yielded 91% of 8. Mechanistic considerations suggested that the deprotective bromination should be improved by replacing the Me3Si by a Me3Ge group. Indeed, bromodegermylation of 1b was quantitative and ca. 60 times faster than bromodesilylation of 1c. The Me3Si and Me3Ge groups can be used for an orthogonal protection/activation of dialkynes. This was shown by desilylating 12 to 11 (Scheme 2), while bromination yielded 13. Both reactions proceeded in high yields; 9 was isolated as a minor by‐product of 13. The reactivity towards bromolysis decreases in the series H‐DOPS > Me3Ge ≈ H > Me3Si > Thp‐DOPS (DOPS = [dimethyl(oxy)‐p ropyl]dimethylsilyl). Orthogonal bromolysis of DOPS‐ and Me3Ge‐substituted dialkynes is slightly more selective than the one of Me3Si‐ and Me3Ge‐substituted analogues. Coupling of 7 with the bromoalkyne 2 gave the dimer 15 (76%), 14 (2%), and 16 (4%) (Scheme 3). The binomial synthesis was optimized so that each cycle, doubling the size of the precursor, requires the minimal number of transformations (Scheme 4). The orthogonally protected monomer 1b, dimer 19, and tetramer 22 were, on the one hand, hydrolyzed to the alcohols 18 (95%), 21 (91%), and 24(91%), respectively, and, on the other hand, bromodegermylated to 2 (99%), 4 (97%), and 6(93%). Cross‐coupling of 18 with 2, 21 with 4, and 24 with 6 gave the orthogonally protected dimer 19 (73%), tetramer 22 (87%), and octamer 25 (83%), respectively.