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

He, Peng; Hu, Mengyang; Zhang, Xinyu; Zhu, Shou‐Fei

doi:10.1055/a-1605-9572

Cited by 37 publications

(16 citation statements)

References 126 publications

(232 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[23][24][25][26] Functionalization of 1,3-enyne, a type of readily available compounds widely used in organic synthesis, has emerged as a powerful method to construct allenyl-and propagyl-derivatives. [27][28][29] However, hydrosilylation reaction of 1,3-enynes remains underdeveloped, in contrast to the signi cant advances in the hydrosilylation of alkenes, [30][31][32][33][34] alkynes [35][36][37][38][39][40] and 1,3-dienes. [41][42][43][44][45][46][47][48][49][50] Such reactions can proceed through three main pathways, including 1,2-/3,4-, [51][52][53][54][55][56][57] and 1,4-hydrosilylations, [58][59][60][61][62] which makes control of regio-, stereo-, and enantioselectivity di cult (Fig.…”

Section: Introductionmentioning

confidence: 99%

Regio- and Enantioselective CuH-Catalyzed 1,2- and 1,4-Hydrosilylation of 1,3-Enynes

Wang

Yang

et al. 2023

Preprint

View full text Add to dashboard Cite

We report a copper-catalyzed ligand-controlled selective 1,2- and 1,4-hydrosilylation of 1,3-enynes, which furnishes enantiomerically enriched propargyl- and 1,2-allenylsilane products in high yields with excellent enantioselectivities (up to 99% ee). This reaction proceeds under mild conditions, shows broad substrate scope for both 1,3-enynes and trihydrosilanes, and displays excellent regioselectivities. Mechanistic studies based on deuterium-labeling reactions and density functional theory (DFT) calculations suggest that allenylcopper is the dominant reactive intermediate under both 1,2- and 1,4-hydrosilylation conditions, and it undergoes metathesis with silanes via selective four-membered or six-membered transition state, depending on the nature of the ligand. The weak interactions between the ligands and the reacting partners are found to be the key controlling factor for the observed regioselectivity switch.

show abstract

Section: Introductionmentioning

confidence: 99%

Regio- and Enantioselective CuH-Catalyzed 1,2- and 1,4-Hydrosilylation of 1,3-Enynes

Wang

Yang

et al. 2023

Preprint

View full text Add to dashboard Cite

show abstract

“…Nevertheless, a greater variety in the strength degrees has been described for the interactions M–HSi than for the M–HC ones . The Si–H bond activation reactions are noticeable because of the relevance of the M–SiR 3 derivatives as intermediate species in the synthesis of chlorosilanes, the SiH/OH coupling, and the hydrosilylation of unsaturated organic substrates, including alkynes …”

Section: Introductionmentioning

confidence: 99%

“… 6 The Si–H bond activation reactions are noticeable because of the relevance of the M–SiR 3 derivatives as intermediate species in the synthesis of chlorosilanes, 7 the SiH/OH coupling, 8 and the hydrosilylation of unsaturated organic substrates, 9 including alkynes. 10 …”

Section: Introductionmentioning

confidence: 99%

“…6 The Si−H bond activation reactions are noticeable because of the relevance of the M−SiR 3 derivatives as intermediate species in the synthesis of chlorosilanes, 7 the SiH/OH coupling, 8 and the hydrosilylation of unsaturated organic substrates, 9 including alkynes. 10 Alkynes are fundamental molecules in organic synthesis, 11 which display great relevance in organometallics due to their use as precursors of different functional groups 12 and as building blocks in the formation of new ligands and interesting metallacycles. 13 Their reactions with transition metal hydride complexes allow for the generation of single, double, and triple M−C bonds, depending on the nature of the metal center, the ligands, and the substituents of the alkyne.…”

Section: ■ Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Silyl-Osmium(IV)-Trihydride Complexes Stabilized by a Pincer Ether-Diphosphine: Formation and Reactions with Alkynes

et al. 2022

View full text Add to dashboard Cite

Complex OsH 4 {κ 3 -P,O,P-[xant(P i Pr 2 ) 2 ]} (1) activates the Si−H bond of triethylsilane, triphenylsilane, and 1,1,1,3,5,5,5-heptamethyltrisiloxane to give the silyl-osmium(IV)trihydride derivatives OsH 3 (SiR 3 ){κ 3 -P,O,P-[xant(P i Pr 2 ) 2 ]} [SiR 3 = SiEt 3 (2), SiPh 3 (3), SiMe(OSiMe 3 ) 2 (4)] and H 2 . The activation takes place via an unsaturated tetrahydride intermediate, resulting from the dissociation of the oxygen atom of the pincer ligand 9,9-dimethyl-4,5-bis(diisopropylphosphino)xanthene (xant-(P i Pr 2 ) 2 ). This intermediate, which has been trapped to form OsH 4 {κ 2 -P,P-[xant(P i Pr 2 ) 2 ]}(P i Pr 3 ) (5), coordinates the Si−H bond of the silanes to subsequently undergo a homolytic cleavage. Kinetics of the reaction along with the observed primary isotope effect demonstrates that the Si−H rupture is the rate-determining step of the activation. Complex 2 reacts with 1,1-diphenyl-2-propyn-1-ol and 1-phenyl-1-propyne. The reaction with the former affords Os{C�CC(OH)Ph 2 } 2 {�C�CHC(OH)Ph 2 }{κ 3 -P,O,P-[xant(P i Pr 2 ) 2 ]} (6), which catalyzes the conversion of the propargylic alcohol into (E)-2-(5,5-diphenylfuran-2(5H)-ylidene)-1,1-diphenylethan-1-ol, via (Z)-enynediol. In methanol, the hydroxyvinylidene ligand of 6 dehydrates to allenylidene, generating Os{C�CC(OH)Ph 2 } 2 {�C�C�CPh 2 }{κ 3 -P,O,P-[xant(P i Pr 2 ) 2 ]} (7). The reaction of 2 with 1-phenyl-1-propyne leads to OsH{κ 1 -C,η 2 -[C 6 H 4 CH 2 CH�CH 2 ]}{κ 3 -P,O,P-[xant(P i Pr 2 ) 2 ]} (8) and PhCH 2 CH�CH(SiEt 3 ).

show abstract

“…During the past several decades, tremendous efforts have been made toward the evolution of the hydrosilylation reaction of unsaturated carbon–carbon bonds. Compared with the great progress of the hydrosilylation reactions of alkenes and alkynes with silanes, the development of the hydrosilylation reactions of conjugated 1,3-dienes was sluggish. The early studies mainly focused on investigating the reactivity of individual examples such as 1,3-pentadiene, isoprene, 1,3-cyclopentadiene, 1,3-cyclohexadiene, and so on.…”

mentioning

confidence: 99%

Copper-Catalyzed Markovnikov Selective 3,4-Hydrosilylation of 2-Substituted 1,3-Dienes

Wang

et al. 2022

Org. Lett.

View full text Add to dashboard Cite

A copper-catalyzed regioselective Markovnikov 3,4-hydrosilylation of 2-substituted 1,3-dienes has been accomplished. A wide range of 2-substituted 1,3-dienes and trihydrosilanes are compatible under the optimal conditions. The bisphosphine ligand with a rigid backbone provides the Markovnikov 3,4-hydrosilylation product in better yield and selectivity. Besides, the synthetic utilities of the allylsilanes also were demonstrated by their flexible derivatizations.

show abstract

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

Cited by 37 publications

References 126 publications

Regio- and Enantioselective CuH-Catalyzed 1,2- and 1,4-Hydrosilylation of 1,3-Enynes

Regio- and Enantioselective CuH-Catalyzed 1,2- and 1,4-Hydrosilylation of 1,3-Enynes

Silyl-Osmium(IV)-Trihydride Complexes Stabilized by a Pincer Ether-Diphosphine: Formation and Reactions with Alkynes

Copper-Catalyzed Markovnikov Selective 3,4-Hydrosilylation of 2-Substituted 1,3-Dienes

Contact Info

Product

Resources

About