Cp2TiCl2-Catalyzed pinacol-type coupling of aliphatic aldehydes by use of zinc and chlorosilane

Hirao, Toshikazu; Hatano, Bunpei; Asahara, Motoki; Muguruma, Yasuaki; Ogawa, Akira

doi:10.1016/s0040-4039(98)01033-8

Cited by 65 publications

(25 citation statements)

References 8 publications

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“…[2,4] Initial efforts in combinatorial chemistry of cubanes have made accelerated discovery of new substances possible. [5] Since this only involves derivatives and not new basic structures, the challenge of finding alternative possibilities for synthesizing new cage compounds remains.…”

Section: Methodsmentioning

confidence: 99%

“…The catalytic cycles known so far allow the use of the catalytic lowvalent metal species down to 1 mol %. [5] The formation of the active coupling reagent takes place by in situ reduction using metals such as manganese, magnesium, or zinc. Fürstner [6] was the first to develop a catalytic reaction by using trimethylsilyl chloride to cleave the metal ± oxygen bond in the intermediate formed.…”

Section: Ulrich Groth* and Mario Jeskementioning

confidence: 99%

See 1 more Smart Citation

Diastereoselective Ce(OiPr)3-Catalyzed Pinacol Couplings of Aldehydes

Groth¹,

Jeske

2000

Angewandte Chemie International Edition

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Section: Methodsmentioning

confidence: 99%

Section: Ulrich Groth* and Mario Jeskementioning

confidence: 99%

Diastereoselective Ce(OiPr)3-Catalyzed Pinacol Couplings of Aldehydes

Groth¹,

Jeske

2000

Angewandte Chemie International Edition

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“…A typical protocol involves the combination of a catalytic amount of a titanium precursor compound, such as Cp 2 TiCl 2 [52][53][54][55][56][57], Cp 2 TiPhCl [58], rac-(EBTHI)TiCl 2 (EBTHI = ethylenebis(η 5 -tetrahydroindenyl) [59], TiCl 3 (THF) 3 [60][61][62][63], or TiCl 4 (THF) 2 [60][61][62][63], with a suitable stoichiometric reductant and a chlorosilane. Pinacol coupling of aromatic aldehydes catalyzed by 3 mol% of Cp 2 TiCl 2 in the presence of MgBr 2 , Me 3 SiCl, and Zn gave 1,2-diols in good yield with high dl-diastereoselectivity (dl:meso ≥ 92:8) [52].…”

Section: Pinacol Coupling Reactionmentioning

confidence: 99%

“…In contrast to the results observed with aromatic aldehydes, catalytic pinacolization of the more difficult to reduce and sterically less biased aliphatic aldehydes and ketones proceeded more sluggishly and rarely exhibited high diastereoselectivity [34,[54][55][56][57].…”

Section: Pinacol Coupling Reactionmentioning

confidence: 99%

Low-Valent Titanium-Mediated Reductive Coupling of Carbonyl Compounds

Ladipo¹

2006

COC

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This account describes recent organic synthesis applications and developments in mechanistic understanding of low-valent titanium-mediated reductive coupling of carbonyl compounds. Pinacol and McMurry coupling reactions are among the most powerful methods for constructing carbon-carbon bonds, and have served as the key step in the synthesis of various natural and synthetic products. The range and selectivity of low-valent titanium reagents that mediate pinacol and McMurry reactions are discussed. The nature of their active species is discussed in conjunction with relevant chemistry of well-characterized low-valent titanium complexes, all of which serve to inform current understanding of the reaction mechanisms.

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“…Such reactions have undergone a significant improvement in recent years. Thus, catalytic pinacolization of aliphatic aldehydes has been performed with Cp 2 TiCl 2 or Cp 2 TiPhCl in the presence of Zn and Me 3 SiCl [244][245][246]. It has been reported that [Cp 2 TiCl] 2 is capable of reductively coupling aromatic and a,b-unsaturated aldehydes to form 1,2-diols in both anhydrous and aqueous media; the measured diastereoselectivity was high, with dl/meso ratios greater than 91:9 [247].…”

Section: Titanium Systemmentioning

confidence: 99%