Selective hydroboration of double bonds in the presence of triple bonds by 9-borabicyclo[3.3.1]nonane. A new route to acetylenic organoboranes and alcohols

Brown, Charles A.; Coleman, Randolph A.

doi:10.1021/jo01327a079

Cited by 62 publications

(30 citation statements)

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“…The differences in reactivities between ethynyl and vinyl groups have been investigated in bromination 19 • 20 and hydroboration. 21 The results indicate that the reactivities of the vinyl compounds were much higher than those of ethynyl compounds. But, the relative reactivity of the radical addition reaction of thiol compounds to ethynyl and vinyl compounds has scarcely been studied.…”

Section: Comparison Between Styrene and Ethynylbenzenementioning

confidence: 92%

Polyaddition of Dithiol Compounds to Diethynyl Compounds: Kinetics of the Model Addition Reaction of Thiophenol to Ethynylbenzene

Kobayashi

Obata

Aoshima

et al. 1990

Polym J

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ABSTRACT:The addition reaction mechanism of thiophenol to ethynylbenzene was studied as a model of the polyaddition of 1,4-benzenedithiol to 1,4-diethynylbenzene. The addition reaction occurred without appreciable side reactions and an adduct of the anti-Markownikoff's structure ( q.,SCH = CHq.,) was quantitatively obtained. It was found that the addition reaction is very similar to the polyaddition of 1,4-benzenedithiol to 1,4-diethynylbenzene from the point of the elementary reaction. The kinetic study shows that the rate-determining step of the addition reaction is the addition reaction of the thiyl radical to the ethynyl bond. The results are compared with those of the addition reaction of thiophenol to styrene.

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Section: Comparison Between Styrene and Ethynylbenzenementioning

confidence: 92%

Polyaddition of Dithiol Compounds to Diethynyl Compounds: Kinetics of the Model Addition Reaction of Thiophenol to Ethynylbenzene

Kobayashi

Obata

Aoshima

et al. 1990

Polym J

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“…It must be noted that internal alkynes are 100 times less reactive than terminal alkenes in related reactions. 17 Therefore, the last result illustrates the high selectivity of the Ni 2 P nanocatalyst towards alkynes vs. alkene. Finally, a retinol derivative containing a conjugated π-system of five alkenes with a single terminal alkyne was hydrogenated to give a reasonable 30% yield of the allalkenyl compound (entry 8).…”

Section: Scope Of the Reactionmentioning

confidence: 86%

Nickel phosphide nanocatalysts for the chemoselective hydrogenation of alkynes

et al. 2012

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Elsevier Carenco, S.; Leyva Perez, A.; Concepción Heydorn, P.; Boissiere, C.; Mezailles, N.; Corma Canós, A. (2012) Well-defined 25 nm nickel phosphide nanoparticles act as a colloidal catalyst for the chemoselective hydrogenation of terminal and internal alkynes. Cis-alkenes are obtained in mild conditions (85°C, a few hours) with good conversion and selectivity. The phosphorus inserted in the Ni-P nanoparticles is critical for the selectivity of the nanocatalyst. Mechanistic investigations support a pre-reduction of the catalyst for its activation. They pinpoint the occurrence of C-H bond cleavage in terminal alkynes during the reaction.

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“…As a byproduct in other processes, it is also easily converted to 9-BBN-H with BMS (eq 17). 22 (17) Efficient procedures have been developed for the preparation of B-Cl-9-BBN from 9-BBN-H (HCl in Et 2 O) 5b and B-Br-9-BBN (BBr 3 in CH 2 Cl 2 ), 23 the latter being a useful reagent for ether cleavage, the bromoboration of 1-alkynes, and for conjugative additions to enones (see 9-Bromo-9-borabicyclo[3.3.1]nonane). 9-BBN triflate is highly useful in formation of enolboranes for stereoselective crossed aldol reactions 24 (see 9-Borabicyclononyl Trifluoromethanesulfonate).…”

Section: %mentioning

confidence: 99%

9-Borabicyclo[3.3.1]nonane Dimer

Soderquist

Roush²,

Heo³

2004

Encyclopedia of Reagents for Organic Synthesis

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InChI = 1/2C8H15B/c2*1-3-7-5-2-6-8(4-1)9-7/h2*7-9H,1-6H2/ t2*7-,8+ InChIKey = FPEQNDQUWPJCKZ-MOGCCKQLBC (highly selective, stable hydroborating agent; 1,3 antiMarkovnikov hydration of alkenes and alkynes; 1d effective ligation for alkyl-, aryl-, allyl-, allenyl-, alkenyl-and alkynylboranes; 1a,4,5 forms stable dialkylboryl derivatives, borinate esters, and haloboranes; 1f organoboranes from hydroboration and organometallic reagents; 1,5 precursor to boracycles; 1,11 can selectively reduce conjugated enones to allylic alcohols; 1a,30 organoborane derivatives for α-alkylation and arylation of α-halo ketones, nitriles, and esters; 1b vinylation and alkynylation of carbonyl compounds; 1a,46 conjugate addition to enones; 1a,47 homologation; asymmetric reduction; Handling, Storage, and Precaution: the crystalline 9-BBN-H dimer can be handled in the atmosphere for brief periods without significant decomposition. However, the reagent should be stored under an inert atmosphere, preferably below 0 • C. Under these conditions the reagent is indefinitely stable. In solution, 9-BBN is more susceptible both to hydrolysis and oxidation, and contact with the open atmosphere should be rigorously avoided. Many 9-BBN derivatives are pyrophoric and/or susceptible to hydrolysis so that individuals planning to use 9-BBN-H dimer should thoroughly familiarize themselves with the special techniques required for the safe handling of such reagents prior to their use. 1b The reagent should be used in a well-ventilated hood.

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Selective hydroboration of double bonds in the presence of triple bonds by 9-borabicyclo[3.3.1]nonane. A new route to acetylenic organoboranes and alcohols

Cited by 62 publications

References 1 publication

Polyaddition of Dithiol Compounds to Diethynyl Compounds: Kinetics of the Model Addition Reaction of Thiophenol to Ethynylbenzene

Polyaddition of Dithiol Compounds to Diethynyl Compounds: Kinetics of the Model Addition Reaction of Thiophenol to Ethynylbenzene

Nickel phosphide nanocatalysts for the chemoselective hydrogenation of alkynes

9-Borabicyclo[3.3.1]nonane Dimer

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