Grignard Synthesis of Alkyl Decaboranes

Gallaghan, John A.; Siegel, Bernard

doi:10.1021/ja01511a064

Cited by 9 publications

(6 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The use of cyclohexane rather than arenes in the cage-opening reaction gave 6-(C 6 H 11 )- nido -B 10 H 13 ( 2 ) in 8% yield, accompanied by 6-(CF 3 SO 3 )- nido -B 10 H 13 derivative 3 (Scheme ). Compound 2 was previously prepared by reacting B 10 H 13 MgBr with cyclohexyl fluoride . The 11 B{H} NMR spectrum of 2 shows seven peaks consistent with the B6-substituted decaborane structure.…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Acid-Induced Opening of [closo-B₁₀H₁₀]^2–as a New Route to 6-Substitutednido-B₁₀H₁₃Decaboranes and Related Carboranes

et al. 2012

View full text Add to dashboard Cite

Protonation of the polyhedral anion [closo-B(10)H(10)](2-) under superacidic conditions apparently generates an electrophilic intermediate, [B(10)H(13)](+), that forms 6-R-nido-B(10)H(13) (R = aryl, alkyl, triflate) derivatives by electrophilic aromatic substitution, C-H bond activation, or ion-pair collapse, respectively. The proposed mechanism of formation of the 6-R-nido-B(10)H(13) derivatives via the boranocation [B(10)H(13)](+) is discussed. The synthesis of carboranes, starting from 6-R-nido-B(10)H(13) decaboranes, and single-crystal X-ray diffraction analyses of several 6-R-nido-B(10)H(13) decaboranes and carboranes are described.

show abstract

Section: Resultsmentioning

confidence: 99%

“…Compound 2 was previously prepared by reacting B 10 H 13 MgBr with cyclohexyl fluoride. 20 The 11 B{H} NMR spectrum of 2 shows seven peaks consistent with the B6substituted decaborane structure. Two sets of broad peaks arising from the cyclohexyl protons resonate at δ 1.67 and 1.18 in the 1 H NMR spectrum.…”

Section: ■ Introductionmentioning

confidence: 95%

Acid-Induced Opening of [closo-B₁₀H₁₀]^2–as a New Route to 6-Substitutednido-B₁₀H₁₃Decaboranes and Related Carboranes

et al. 2012

View full text Add to dashboard Cite

show abstract

“…Benzyl chloride reacts with B 10 H 13 MgI to form 6-benzyldecaborane and with alkyl fluorides to form the corresponding allyl- and alkyl decaboranes, though the alkylation sites are not known.…”

Section: Introductionmentioning

confidence: 99%

Monoalkyldecaborane(14) Syntheses via Nucleophilic Alkylation and Hydroboration

et al. 1998

View full text Add to dashboard Cite

Two regioselective, high-yield routes to nido-6-alkyldecaborane(14)s via one-pot syntheses are reported. Alkyllithium reagents add to salts of nido-B(10)H(13)(-) to form arachno-6-R-B(10)H(13)(2)(-), which may be protonated using HCl/Et(2)O, first to the corresponding arachno-6-R-B(10)H(14)(-) anion and then, with H(2) loss, to nido-6-R-B(10)H(13). Alternately, olefin hydroboration of arachno-6,9-(SMe(2))(2)-B(10)H(12) produces nido-6-R-8-(SMe(2))-B(10)H(11), which may be reduced, using Superhydrid, to nido-6-R-B(10)H(12)(-), and then protonated with HCl/Et(2)O to nido-6-R-B(10)H(13). X-ray diffraction studies of the following intermediates and products are presented: nido-8-(SMe(2))-B(10)H(12), nido-6-Thx-8-(SMe(2))-B(10)H(11), and nido-6-Thx-B(10)H(13).

show abstract

“…41kyl pentaborane-9 and alkyldecaborane derivatives have been synthesized by methods not involving other alkylboron compounds as reagents (17,18,19). Since the less stable hydrides, tetraborane, B4H10, and dihydropentaborane or pentaborane-11, B5Hll, could scarcely be alkylated by such drastic nleans, though diineth] leiletetraborane is made in the hot-cold reactor (20) The results obtained illustrate that these alkylation reactions, like those of the diboranes, proceed in conforlllance with the analogies suggested by the exchange processes.…”

mentioning

confidence: 99%

Observations on Alkylboranes

Lutz¹,

Ritter²

1963

Can. J. Chem.

View full text Add to dashboard Cite

Some synthesis and exchange reactions of diborarle and its allcyl derivatives and of the higher boron hydrides were reviewed as baclrground for new work.In pursuit of an idea prorripted by knowledge of the deuterium and BI0 exchanges found for the reactive and unstable higher boron hydrides and BeH11, mono-and di-methyldih y d r~~e n t a b o r a n e arid methyltetraborane ha\-e been prepared by direct reaction between the parent higher hydrides and 1,2-dimethyldiborane or monomethyldiborane. The identity and the reactions of each product have been delineated by gas chromatographic separation, gas density, and mass, infrared, and 1l.m.r. spectrotnetry. The H' n.ni.r. spectrum of dihydro~e n t a b o r a n e has been reinterpreted and used to decide that monomethyldihydrope~ltaborane is probably a B 111 derivative which displays stereolsomerism.T o confine the topic within proportioils suitable for a symposium this paper concerns mostly alkylation reactions in which carbon atoms are transferred fronl sites in one boron coillpound to sites in another, thus excluding allnost conlpletely the extensive material on hq droborntion.As a preliminary, coilsider some facts about the boron hydrides. They occur in two types, the open pqramidal and the closed pqrainidal structures, with the commonest members, diborane, tetraborane-10, pentaborane-11, as examples of the first class and pentaborane-9 and decaborane-14 of the second. The former are the labile, reactive hydrides, the latter the ones of lesser reactivity. Exchange and interconversion reactions show the labile hydrides to maintain effective steady-state concentrations of reactive f r a g m e n t s~ the more stable ones do not (1, 2).Diboraile is convertible to the other hydrides by pyrolysis (3) and by interactions such as that with tetraborane (4):Three boron and deuterium exchanges-exemplify models for alkylation reactions: (a) self-exchange of diborane, (b) diborane exchange with pentaborane-9, and (c) diborane exchange with pentaborane-11. The first is 3/2 order involving successively dissociation of diborane and a borane-diborane displacement reaction with E* = 22 kcal. Deuterium exchanges three times faster than boron. Similarly, the second is 1/2 order in diborane (dissociation) and first order with respect to pentaborane-9, but without boron exchange, E+ = 27 kcal. Since the third, pentaborane-11 -diborane exchange, is 1/2 order with respect to the higher hydride and first order in diborane the dissociation is that of pentaborane-11 and the displacement is borane-diborane. With these varying patterns 'Presented at the Synzposium on Organometallic Compounds, Vancouver, British Columbia, September 4-6, 1962, sponsored

show abstract

Grignard Synthesis of Alkyl Decaboranes

Cited by 9 publications

References 0 publications

Acid-Induced Opening of [closo-B₁₀H₁₀]^2–as a New Route to 6-Substitutednido-B₁₀H₁₃Decaboranes and Related Carboranes

Acid-Induced Opening of [closo-B₁₀H₁₀]^2–as a New Route to 6-Substitutednido-B₁₀H₁₃Decaboranes and Related Carboranes

Monoalkyldecaborane(14) Syntheses via Nucleophilic Alkylation and Hydroboration

Observations on Alkylboranes

Contact Info

Product

Resources

About

Grignard Synthesis of Alkyl Decaboranes

Cited by 9 publications

References 0 publications

Acid-Induced Opening of [closo-B10H10]2–as a New Route to 6-Substitutednido-B10H13Decaboranes and Related Carboranes

Acid-Induced Opening of [closo-B10H10]2–as a New Route to 6-Substitutednido-B10H13Decaboranes and Related Carboranes

Monoalkyldecaborane(14) Syntheses via Nucleophilic Alkylation and Hydroboration

Observations on Alkylboranes

Contact Info

Product

Resources

About

Acid-Induced Opening of [closo-B₁₀H₁₀]^2–as a New Route to 6-Substitutednido-B₁₀H₁₃Decaboranes and Related Carboranes

Acid-Induced Opening of [closo-B₁₀H₁₀]^2–as a New Route to 6-Substitutednido-B₁₀H₁₃Decaboranes and Related Carboranes