Metal mediated carbometallation of alkynes and alkenes containing adjacent heteroatoms

Fallis, Alex G.; Forgione, Pat

doi:10.1016/s0040-4020(01)00422-7

Cited by 171 publications

(61 citation statements)

References 68 publications

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“…Based on the structure of the products Z-2, the Btype intermediate D was proposed, which may undergo coupling reaction with allyl bromide [5a,10] or PhI (catalyzed by PdA C H T U N G T R E N N U N G (PPh 3 ) 4 ) [11] to afford the corresponding coupling products 4a and 6a smoothly in 55 % and 56 % isolated yields, respectively (Scheme 3).…”

Section: Resultsmentioning

confidence: 99%

“…[4] In the hydro-or carbometalation reaction of primary propargylic alcohols, the alkyl or H group from the organometallic reagent was highly regio-and stereoselectively introduced into the 2-position of propargylic alcohols probably due to the favorable formation of the 5-membered metallacyclic intermediate affording the 3-iodo-2(E)-propenols A upon quenching with I 2 (Scheme 1). [5,6] However, for secondary or tertiary alcohols the carbometalation afforded regioisomeric mixtures of isomers A (branched) and C (linear) depending on the reaction conditions.…”

Section: Introductionmentioning

confidence: 99%

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Copper(I)‐Mediated Highly Stereoselective syn‐Carbometalation of Secondary or Tertiary Propargylic Alcohols with Primary Grignard Reagents in Toluene with a High Linear Regioselectivity

Ma¹,

Lu²

2006

Adv Synth Catal

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Abstract:A highly regio-and stereoselective syn-carbometalation of terminal secondary or tertiary propargylic alcohols with primary alkyl Grignard reagents in toluene or phenylmagnesium bromide in Et 2 O was developed, in which the alkyl or phenyl group from the Grignard reagents is introduced into the terminal position of the alcohols. The organometallic intermediate formed may be used directly for the coupling reaction with organic halides. Upon treatment with I 2 after the carbometalation, iodides may be obtained, which may undergo Sonogashira coupling reaction and highly stereoselective Novozym-435-catalyzed kinetic resolution to afford the optically active products.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Copper(I)‐Mediated Highly Stereoselective syn‐Carbometalation of Secondary or Tertiary Propargylic Alcohols with Primary Grignard Reagents in Toluene with a High Linear Regioselectivity

Ma¹,

Lu²

2006

Adv Synth Catal

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“…These results clearly implicate the strong directing effect (CIPE) of the 2-pyridyl group on silicon in the alkynylsilane structure to achieve this Cu-catalyzed carbomagnesation reaction (Scheme 8). 26 Moreover, control experiments indicate that this carbometalation proceeds not through organocopper species but rather through organocuprate species 22 generated in situ.…”

Section: Carbomagnesation Across Alkynyl(2-pyridyl)silanesmentioning

confidence: 99%

2-Pyridylsilyl Group: A Useful Multifunctional Group in Organic Synthesis

Itami¹,

Yoshida²

2006

Synlett

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The utility of the 2-pyridylsilyl group as a multifunctional group in organic synthesis is described. The use of the 2-pyridylsilyl group as a removable directing group is a powerful synthetic strategy that circumvents the specificity-generality dilemma in metal-mediated organic synthesis. In addition, the utility of the 2pyridylsilyl group as a phase tag for strategic separation and as a removable hydrophilic group for aqueous reactions is also described.

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“…Pertinent analyses of conceivable strategies and representative illustrations involving Pd (and Pt) [5,21], Ni [22,23], and other metals [24] can be found in recent reviews. Again, palladium reagents are particularly well suited for such tranformations.…”

Section: Carbometallation Of Alkynesmentioning

confidence: 99%