Platinum‐Catalyzed Hydrosilylations of Internal Alkynes: Harnessing Substituent Effects to Achieve High Regioselectivity

Rooke, Douglas A.; Ferreira, E.

doi:10.1002/anie.201108714

Cited by 107 publications

(33 citation statements)

References 36 publications

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“…The observed regioselectivity can be ascribed to a selective attack of the nucleophilic oxidant to the more electrophilic distal C(sp). Notably, a recently published Pt-catalyzed hydrosilylation on a similar substrate showed a 3.7:1 regioselectivity [42]. This unexpectedly high selectivity with gold catalysis is attributed to the augmentation of the electronic bias of the C–C triple bond via the gold activation.…”

Section: Resultsmentioning

confidence: 95%

Gold-catalyzed regioselective oxidation of propargylic carboxylates: a reliable access to α-carboxy-α,β-unsaturated ketones/aldehydes

Ji¹,

Nelson²,

Zhang³

2013

Beilstein J. Org. Chem.

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SummaryGold-catalyzed intermolecular oxidation of carboxylates of primary or secondary propargylic alcohols are realized with excellent regioselectivity, which is ascribed to inductive polarization of the C–C triple bond by the electron-withdrawing carboxy group. The gold carbene intermediates thus generated undergo selective 1,2-acyloxy migration over a 1,2-C–H insertion, and the selectivities could be dramatically improved by the use of a P,S-bidentate ligand, which is proposed to enable the formation of tris-coordinated and hence less electrophilic gold carbene species. α-Carboxy α,β-unsaturated ketones/aldehydes can be obtained with fair to excellent yields.

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Section: Resultsmentioning

confidence: 95%

Gold-catalyzed regioselective oxidation of propargylic carboxylates: a reliable access to α-carboxy-α,β-unsaturated ketones/aldehydes

Ji¹,

Nelson²,

Zhang³

2013

Beilstein J. Org. Chem.

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“…[1] Consequently,t he hydrosilylation of alkynes, arguably the most direct and atom-economical route to vinyl silanes,h as become an area of intense investigation in the past few decades. Moreover, almost all previous studies on this topic have been focused on electron-normal [2,3] and electron-deficient [4] alkynes (Scheme 1a). Moreover, almost all previous studies on this topic have been focused on electron-normal [2,3] and electron-deficient [4] alkynes (Scheme 1a).…”

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confidence: 99%

Highly Regio‐ and Stereoselective Hydrosilylation of Internal Thioalkynes under Mild Conditions

et al. 2015

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A general and mild hydrosilylation of thioalkynes is described. With the cationic catalyst [Cp*Ru(MeCN)3 ](+) and the bulky silane (TMSO)3 SiH, a range of thioalkynes underwent smooth hydrosilylation at room temperature with excellent α regioselectivity and syn stereoselectivity. DFT calculations provided important insight into the mechanism, particularly the unusual syn selectivity with the [Cp*Ru(MeCN)3 ](+) catalyst. The sulfenyl group in the substrates was found to provide important chelation stabilization to direct the reaction through a new mechanistic pathway.

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“…Both the Lindlar and the Boland reduction on 19 and its triol failed to give the desired ethyl ester of 2 , contrary to earlier reports on similar internal alkynes . The Karstedt alkyne hydrosilylation/proto‐desilylation protocol is an alternative to the Z ‐selective reduction of internal alkynes for making cis ‐olefins . To our knowledge, this protocol has been utilized only once in a total synthesis of a natural product .…”

Section: Figurementioning

confidence: 78%

Resolving Inflammation: Synthesis, Configurational Assignment, and Biological Evaluations of RvD1_n−3 DPA

Tungen

Gerstmann

Vik

et al. 2018

Chemistry A European J

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New drugs that can resolve inflammation without immunosuppressive effects are at the medicinal chemistry frontier. Pro‐resolving endogenously formed small molecules, that is, the resolvins, are excellent candidates displaying such bioactions. The first total synthesis of the specialized pro‐resolving mediator RvD1n−3 DPA has been achieved using the underutilized sp3–sp3 Negishi cross coupling reaction and an alkyne hydrosilylation–protodesilylation protocol. Biological evaluations revealed that this novel mediator displays low nanomolar pro‐resolving properties and potently activates the human DRV1/GPR32 receptor. As such, this endogenous natural product is a lead compound for the development of novel immunoresolvents.

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Platinum‐Catalyzed Hydrosilylations of Internal Alkynes: Harnessing Substituent Effects to Achieve High Regioselectivity

Cited by 107 publications

References 36 publications

Gold-catalyzed regioselective oxidation of propargylic carboxylates: a reliable access to α-carboxy-α,β-unsaturated ketones/aldehydes

Gold-catalyzed regioselective oxidation of propargylic carboxylates: a reliable access to α-carboxy-α,β-unsaturated ketones/aldehydes

Highly Regio‐ and Stereoselective Hydrosilylation of Internal Thioalkynes under Mild Conditions

Resolving Inflammation: Synthesis, Configurational Assignment, and Biological Evaluations of RvD1_n−3 DPA

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Platinum‐Catalyzed Hydrosilylations of Internal Alkynes: Harnessing Substituent Effects to Achieve High Regioselectivity

Cited by 107 publications

References 36 publications

Gold-catalyzed regioselective oxidation of propargylic carboxylates: a reliable access to α-carboxy-α,β-unsaturated ketones/aldehydes

Gold-catalyzed regioselective oxidation of propargylic carboxylates: a reliable access to α-carboxy-α,β-unsaturated ketones/aldehydes

Highly Regio‐ and Stereoselective Hydrosilylation of Internal Thioalkynes under Mild Conditions

Resolving Inflammation: Synthesis, Configurational Assignment, and Biological Evaluations of RvD1n−3 DPA

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Resolving Inflammation: Synthesis, Configurational Assignment, and Biological Evaluations of RvD1_n−3 DPA