Construction of highly sterically hindered 1,1-disilylated terminal alkenes

Zhang, Xueyan; Ji, Xin; Xie, Xingze; Ding, Shengtao

doi:10.1039/c8cc07765g

Cited by 15 publications

(6 citation statements)

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“…Non-protected and protected homopropargyl alcohols could likewise participate in this hydrosilylation process smoothly (14)(15)(16). The regioselectivity deteriorated slightly in the hydrosilylation of alkynyl alcohol or acid substrates with extended main chains (17)(18)(19). Replacement of hydroxyl group with aryl group led to decreased regioselectivity as well (20).…”

Section: Resultsmentioning

confidence: 99%

“…In recent years, this problem has been partially addressed with the developments of several efficient protocols . For instance, Ru-based complexes have been developed as the predominant catalysts for this field since the pioneering works from Trost and Yamamoto, et al [3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18] . Co-catalyzed α-hydrosilylation of alkynes showed superiority in modification of aryl alkynes [19][20][21][22][23] .…”

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confidence: 99%

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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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Section: Resultsmentioning

confidence: 99%

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confidence: 99%

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

et al. 2019

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“…When silyl acetylenes were used, the reaction was electronically induced to produce highly sterically hindered 1,1-disilylated terminal alkenes with specific regioselectivity (Table 5, entry 1). 22,[98][99][100] In addition, Cp*RuH 3 (PR 3 ) and Grubbs' I catalyst also enabled -selective hydrosilylation of alkyl acetylenes (entries 2-3). 101,102 Rh-and Pt-catalyzed -selective hydrosilylation reactions of terminal alkynes were not as effective as in -selective hydrosilylation reactions (entries 4-7).…”

Section: Synthesismentioning

confidence: 99%

Transition-Metal-Catalyzed Stereo- and Regioselective Hydrosilylation of Unsymmetrical Alkynes

He¹,

Hu²,

Zhang³

et al. 2021

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“…So far, metal catalysts effecting selective anti -Markovnikov hydrosilylation of alkynes to form β-vinylsilanes have been well developed. − However, the reported metal-catalyzed Markovnikov hydrosilylation reactions of alkynes to yield α-vinylsilanes generally suffer from limited substrate scope and/or poor α / β selectivity. − For example, the Karstedt’s catalyst Pt 2 ((CH 2 CHSiMe 2 ) 2 O) 3 at high temperature (110 °C) can effectively catalyze the hydrosilylation reactions of terminal alkynes with tertiary silanes to afford α-vinylsilanes as the major product . The α / β -selectivity of this platinum-catalyzed reaction, however, is merely in the range 6:1 to 1:1 (eq 1 in Figure b).…”

Section: Introductionmentioning

confidence: 99%

Markovnikov Hydrosilylation of Alkynes with Tertiary Silanes Catalyzed by Dinuclear Cobalt Carbonyl Complexes with NHC Ligation

et al. 2021

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Metal-catalyzed hydrosilylation of alkynes is an ideal atom-economic method to prepare vinylsilanes that are useful reagents in the organic synthesis and silicone industry. Although great success has been made in the preparation of β-vinylsilanes by metal-catalyzed hydrosilylation reactions of alkynes, reported metal-catalyzed reactions for the synthesis of α-vinylsilanes suffer from narrow substrate scope and/or poor selectivity. Herein, we present selective Markovnikov hydrosilylation reactions of terminal alkynes with tertiary silanes using a dicobalt carbonyl N-heterocyclic carbene (NHC) complex [(IPr) 2 Co 2 (CO) 6 ] (IPr = 1,3-di(2,6-diisopropylphenyl)imidazol-2-ylidene) as catalyst. This cobalt catalyst effects the hydrosilylation of both alkyl-and aryl-substituted terminal alkynes with a variety of tertiary silanes with good functional group compatibility, furnishing α-vinylsilanes with high yields and high α/β selectivity. Mechanistic study revealed that the stoichiometric reactions of [(IPr) 2 Co 2 (CO) 6 ] with PhCCH and HSiEt 3 can furnish the dinuclear cobalt alkyne and mononuclear cobalt silyl complexes [(IPr)(CO) 2 Co(μ−η 2 :η 2 -HCCPh)Co(CO) 3 ], [(IPr)(CO) 2 Co(μ-η 2 :η 2 -HCCPh)Co(CO) 2 (IPr)], and [(IPr)Co(CO) 3 (SiEt 3 )], respectively. Both dicobalt bridging alkyne complexes can react with HSiEt 3 to yield α-triethylsilyl styrene and effect the catalytic Markovnikov hydrosilylation reaction. However, the mono(NHC) dicobalt complex [(IPr)(CO) 2 Co(μ-η 2 :η 2 -HCCPh)Co(CO) 3 ] exhibits higher catalytic activity over the di(NHC)-dicobalt complexes. The cobalt silyl complex [(IPr)Co(CO) 3 (SiEt 3 )] is ineffective in catalyzing the hydrosilylation reaction. Deuterium labeling experiments with PhCCD and DSiEt 3 indicates the synaddition nature of the hydrosilylation reaction. The absence of deuterium scrambling in the hydrosilylation products formed from the catalytic reaction of PhCCH with a mixture of DSiEt 3 and HSi(OEt) 3 hints that mononuclear cobalt species are less likely the in-cycle species. These observations, in addition to the evident of nonsymmetric Co 2 C 2 -butterfly core in the structure of [(IPr)(CO) 2 Co(μ-η 2 :η 2 -HCCPh)Co(CO) 3 ], point out that mono(IPr)-dicobalt species are the genuine catalysts for the cobaltcatalyzed hydrosilylation reaction and that the high α selectivity of the catalytic system originates from the joint play of the dicobalt carbonyl species to coordinate alkynes in the Co(μ-η 2 :η 2 -HCCR′)Co mode and the steric demanding nature of IPr ligand.

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Construction of highly sterically hindered 1,1-disilylated terminal alkenes

Abstract: One direct and efficient procedure for the synthesis of 1,1-disilylated terminal alkenes is demonstrated.

Cited by 15 publications

References 71 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

Transition-Metal-Catalyzed Stereo- and Regioselective Hydrosilylation of Unsymmetrical Alkynes

Markovnikov Hydrosilylation of Alkynes with Tertiary Silanes Catalyzed by Dinuclear Cobalt Carbonyl Complexes with NHC Ligation

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