Iridium-Catalyzed Hydrosilylation of Unactivated Alkenes: Scope and Application to Late-Stage Functionalization

Xie, Xingze; Zhang, Xueyan; Yang, Haoyu; Ji, Xin; Li, Jianing; Ding, Shengtao

doi:10.1021/acs.joc.8b02838

Cited by 35 publications

(40 citation statements)

References 44 publications

(61 reference statements)

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“…For instance, -OSiMe 2 (vinyl) was successfully anchored to replace the -OTMS group, which could be further decorated by other means (Fig. 4c) 68 .…”

Section: Resultsmentioning

confidence: 99%

Iridium-catalyzed Markovnikov hydrosilylation of terminal alkynes achieved by using a trimethylsilyl-protected trihydroxysilane

et al. 2019

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Developing efficient strategies for Markovnikov hydrosilylation of alkynes is still an important goal. The steric and electronic properties of hydrosilanes are key factors in controlling selectivity in these reactions. Here by using a trimethylsilyl-protected trihydroxysilane, we report a mild, efficient strategy for Markovnikov hydrosilylation of terminal alkynes with the simple catalyst [Ir(μ-Cl)(cod)] 2 . A variety of terminal alkynes are hydrosilylated efficiently with outstanding α-regioselectivity. This protocol is successfully utilized in the late-stage hydrosilylation of derivatives of various bio-relevant molecules. The residual silyl group, -Si (OSiMe 3 ) 3 , can participate in organic transformations directly, or be converted into other useful silyl groups.

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“…For instance, -OSiMe 2 (vinyl) was successfully anchored to replace the -OTMS group, which could be further decorated by other means (Fig. 4c) 68 .…”

Section: Resultsmentioning

confidence: 99%

Iridium-catalyzed Markovnikov hydrosilylation of terminal alkynes achieved by using a trimethylsilyl-protected trihydroxysilane

et al. 2019

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“…A recent report from Ding's group illustrated the high efficiency of [(COD)IrCl] 2 in hydrosilylating various functionalized 1-alkenes under simple and mild conditions (Scheme 15). 28 A variety of allyl ether substrates, including derivatives from naturally available compounds, could be smoothly hydrosilylated to afford the desired products 7-11 in moderate to excellent yields.…”

Section: Scheme 14 Reactions Between Alkynylsilanes and Alkenes Catalmentioning

confidence: 99%

“…30 Similar research was also conducted by Ding's group without using COD as an additive (Scheme 18). 28 As simple aryl and alkyl substrates have been studied by Shimada, Ding et al devoted more efforts towards the investigation of more complicated compounds. Diverse N-heterocycles were well tolerated in this process to afford products 27-30.…”

Section: Scheme 15 Hydrosilylation Of Allyl Ether Derivatives By [(Comentioning

confidence: 99%

“…Unlike the mechanism mentioned in Kühn's work (Scheme 13), the generation of iridium(I) hydride A is proposed as the initial step, which is supported by theoretical and experimental studies. 28,30,31 Intermediates C and D, formed in the hydrometallation and oxidative addition steps, could be stabilized by the coordination of sulfur with the metal center. It is noteworthy that this mechanism involving an Ir(I) Ding and co-workers also investigated the hydrosilylation of 1,1-disubstituted alkenes in their later research, which is much more challenging since increased steric hindrance will hamper coordination of the alkene with the catalyst.…”

Section: Scheme 18 Hydrosilylation Of Sulfur-containing Olefins With mentioning

confidence: 99%

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Progress on Iridium-Catalyzed Hydrosilylation of Alkenes and Alkynes

Gao

Ding

2020

Synthesis

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Hydrosilylation of multiple carbon–carbon bonds is a well-known process for the construction of organosilicon compounds. Nowadays, precious metal catalysts, especially platinum complexes, still occupy dominant positions in such processes. However, one important member of the precious metal family, iridium, is less used in this field. As early research mainly focused on developing stable and effective iridium catalysts, recent advances have disclosed the specific efficiency of simple iridium catalytic systems in the synthesis of functional organosilicon compounds. This short review summarizes the utilization of iridium complexes for the hydrosilylation of alkenes and alkynes, with an emphasis on the recent advances published in the last decade.1 Introduction2 Iridium-Catalyzed Hydrosilylation of Alkenes3 Iridium-Catalyzed Hydrosilylation of Alkynes4 Conclusions and Perspectives

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“…Recent studies in this field involve the development of catalysts that facilitate hydrosilylation at olefin or carbonyl moieties while excluding other functional groups, such as halides and hydroxy groups from the reaction. These chemoselective hydrosilylation reactions have been reported for olefin bearing halogen, [1,2,[3][4][5][6] hydroxy, [4,7] carbonyl, [3,[7][8][9] epoxy, [1,3,5,7,10] amino, [1,3,6,11] and sulfide [5,12] substituents. Hydrosilylation reactions of unsaturated organic compounds such as olefins and ketones (aldehydes) are commonly and widely used in the industry.…”

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Chemoselective Hydrosilylation of Olefin/Ketone Catalyzed by Iminobipyridine Fe and Co complexes

et al. 2019

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The chemoselective hydrosilylation of olefins and ketones catalyzed by Fe and Co complexes bearing an iminobipyridine derivative ligand was investigated. The reaction of a 1 : 1 mixture of styrene and acetophenone over the Fe catalyst achieved selective hydrosilylation of acetophenone. In contrast, the corresponding Co complex showed the opposite selectivitystyrene-selective hydrosilylation. The reaction of 3-acetylstyrene with both olefin and ketone moieties in the molecule showed that the Co complex catalyzed olefin-selective hydrosilylation. In contrast, the addition of pyridine to the Co-catalyzed system showed the opposite chemoselectivity, affording the ketone hydrosilylated product. The chemoselectivity of olefin/ketone hydrosilylation was switched by replacing the central metal of the complex with the iminobipyridine derivative ligand and by changing the simple reaction conditions (absence or presence of pyridine) using an identical Co complex.Hydrosilylation is widely used to obtain organosilane compounds, and many catalysts for hydrosilylation have been developed to date. Recent studies in this field involve the development of catalysts that facilitate hydrosilylation at olefin or carbonyl moieties while excluding other functional groups, such as halides and hydroxy groups from the reaction. These chemoselective hydrosilylation reactions have been reported for olefin bearing halogen, [1,2,[3][4][5][6] hydroxy, [4,7] carbonyl, [3,[7][8][9] epoxy, [1,3,5,7,10] amino, [1,3,6,11] and sulfide [5,12] substituents. Hydrosilylation reactions of unsaturated organic compounds such as olefins and ketones (aldehydes) are commonly and widely used in the industry. However, the chemoselective hydrosilylation of olefins and ketones is challenging. For compounds containing both olefin and ketone moieties, several reactions have demonstrated olefin [1,[7][8][9] and ketone selectivity [13] . To exhibit selectivity, each catalyst has its own distinctive ligand; however, catalysts with selectivity for olefin/ketone hydrosilylation that can be converted by simply changing the reaction conditions have not been reported to date.Recently, iron complexes with an iminobipyridine derivative ligand (Figure 1) have been reported to exhibit high catalytic activity for hydrosilylation of olefin [14] and ketone [15] with a much higher catalytic activity for ketone than that for olefin. [15] In addition, the addition of pyridine to the iron-catalyzed system accelerated ketone hydrosilylation, whereas it suppressed the olefin hydrosilylation. [15] These results suggest that a transition metal complex with higher catalytic activity for olefins than that for ketones could be developed. Moreover, the catalytic activity for ketones could be enhanced and that for olefins suppressed by the addition of a pyridine, similar to the iron system. Moreover, the chemoselectivity of olefin/ketone hydrosilylation could be switched by the simple addition of pyridine using the same catalyst.This paper reports (i) the preparation of novel Co complexes be...

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Iridium-Catalyzed Hydrosilylation of Unactivated Alkenes: Scope and Application to Late-Stage Functionalization

Cited by 35 publications

References 44 publications

Iridium-catalyzed Markovnikov hydrosilylation of terminal alkynes achieved by using a trimethylsilyl-protected trihydroxysilane

Iridium-catalyzed Markovnikov hydrosilylation of terminal alkynes achieved by using a trimethylsilyl-protected trihydroxysilane

Progress on Iridium-Catalyzed Hydrosilylation of Alkenes and Alkynes

Chemoselective Hydrosilylation of Olefin/Ketone Catalyzed by Iminobipyridine Fe and Co complexes

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