Enantioselective radical-chain hydrosilylation of alkenes using homochiral thiols as polarity-reversal catalysts

Haque, Muhammed; Roberts, Brian P.; Tocher, Derek A.

doi:10.1039/a803280g

Cited by 78 publications

(55 citation statements)

References 30 publications

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“…A similar catalytic phenomenon has been described by Crich and co-workers for reactions involving stannanes catalyzed by benzeneselenol, a technique that effectively extends the kinetic range of stannane-mediated reactions [8]. It is interesting to note that Roberts showed that alkenes could be easily hydrosilylated by using silane/thiol mixtures [9].…”

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confidence: 80%

Polarity‐Reversal‐Catalyzed Hydrostannylation Reactions: Benzeneselenol‐Mediated Homolytic Hydrostannylation of Electron‐Rich Olefins

Ford

Wille

Schiesser

2006

Helvetica Chimica Acta

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Dedicated to the memory of Professor Hanns Fischer. We take for granted his many contributions to the field of radical chemistry. I am particularly indebted to his careful and patient explaining to me of the persistent radical effect over a drink, on a balmy New Hampshire evening.Addition of 10 mol-% of diphenyl diselenide to hydrostannylation reactions involving electron-rich olefins results in a dramatic improvement in yield. For example, reaction of a-{[(tert-butyl)dimethylsilyl]-A C H T U N G T R E N N U N G oxy}styrene (1) with triphenylstannane (2a; 1.1 equiv.) in the presence of PhSeSePh and 2,2'-azobis[2-methylpropanenitrile] (AIBN) affords {2-{[(tert-butyl)dimethylsilyl]oxy}-2-phenylethyl}triphenylstan-nane (3a) in 95% yield after 2 h. This reaction presumably benefits, by the increased rate of H-atom transfer, from the in situ generated polarity-reversal catalyst, benzeneselenol.

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confidence: 80%

Polarity‐Reversal‐Catalyzed Hydrostannylation Reactions: Benzeneselenol‐Mediated Homolytic Hydrostannylation of Electron‐Rich Olefins

Ford

Wille

Schiesser

2006

Helvetica Chimica Acta

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“…Roberts and co-workers have employed a number of chiral carbohydratederived thiols as polarity reversal catalysts in the radical hydrosilylation of electron-rich prochiral alkenes [68][69][70]. In these thiols, the SH group is attached to the anomeric carbon atom.…”

Section: Polarity-reversal Catalysismentioning

confidence: 98%

Enantioselective Radical Reactions

Zimmerman

Sibi

2006

Radicals in Synthesis I

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“…(1)]. [10] Although asymmetric hydrogenation, [11] dihydroxylation, [12] hydroamination, [13] and hydroboration [14] of simple 1,1-disubstituted alkenes have been recently achieved with greater than or equal to 90 % ee, to the best of our knowledge, there have not been any reports of a general method for the highly enantioselective hydrosilylation of 1,1-disubstituted alkenes. [7] Bosnich and co-workers [8] also described a similar rhodium-catalyzed intramolecular asymmetric hydrosilylation of olefins with higher reactivities and a broader substrate scope, however, low enantioselectivities (0.7-60 % ee) were observed in the cases of asymmetric hydrosilylation of 1,1-disubstituted alkenes.…”

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confidence: 99%