Enantioselective Synthesis of 6/5-Spirosilafluorenes by Asymmetric Ring Expansion of 4/5-Spirosilafluorenes with Alkynes

Chen, Hua; Zhang, Haixia; Du, Huimin; Kuang, Yuzhong; Pang, Qinjiao; L, Gao; Wang, Wanshu; Yang, Cheng; Song, Zhenlei

doi:10.1021/acs.orglett.3c00346

Cited by 16 publications

(5 citation statements)

References 41 publications

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“…Compound (R)-270 was prepared from (R)-269 to catalyze the asymmetric ring expansion of cyclic silanes with alkynes in the presence of [Rh(CH 2 �CH 2 ) 2 Cl] 2 . 317 Similar to the synthesis of (R)-269, compounds (S)-271a−d were synthesized from the reaction of the ortho-lithiated (S)-BINOL-MOM with the fluorinated arenes followed by removal of the MOM groups with HCl/ MeOH under refluxing. 318 These compounds were converted to the phosphoric acids (S)-272 to catalyze the asymmetric αhydroxylation of α-branched cyclic ketones with PhNO.…”

Section: Reactions Of Binol Methoxymethyl Ethermentioning

confidence: 99%

“… , After removal of the MOM groups, it was used to catalyze the asymmetric vinyl boronic acid addition to enones. Compound ( R )- 270 was prepared from ( R )- 269 to catalyze the asymmetric ring expansion of cyclic silanes with alkynes in the presence of [Rh(CH 2 CH 2 ) 2 Cl] 2 . Similar to the synthesis of ( R )- 269 , compounds ( S )- 271a – d were synthesized from the reaction of the ortho-lithiated ( S )-BINOL-MOM with the fluorinated arenes followed by removal of the MOM groups with HCl/MeOH under refluxing .…”

Section: Ortho-lithiation At 3-positionmentioning

confidence: 99%

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Regioselective Substitution of BINOL

2024

Chem. Rev.

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1,1′-Bi-2-naphthol (BINOL) has been extensively used as the chirality source in the fields of molecular recognition, asymmetric synthesis, and materials science. The direct electrophilic substitution at the aromatic rings of the optically active BINOL has been developed as one of the most convenient strategies to structurally modify BINOL for diverse applications. High regioselectivity has been achieved for the reaction of BINOL with electrophiles. Depending upon the reaction conditions and substitution patterns, various functional groups can be introduced to the specific positions, such as the 6-, 5-, 4-, and 3-positions, of BINOL. Ortho-lithiation at the 3-position directed by the functional groups at the 2-position of BINOL have been extensively used to prepare the 3- and 3,3′-substituted BINOLs. The use of transition metal-catalyzed C–H activation has also been explored to functionalize BINOL at the 3-, 4-, 5-, 6-, and 7-positions. These regioselective substitutions of BINOL have allowed the construction of tremendous amount of BINOL derivatives with fascinating structures and properties as reviewed in this article. Examples for the applications of the optically active BINOLs with varying substitutions in asymmetric catalysis, molecular recognition, chiral sensing and materials are also provided.

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Section: Reactions Of Binol Methoxymethyl Ethermentioning

confidence: 99%

Section: Ortho-lithiation At 3-positionmentioning

confidence: 99%

Regioselective Substitution of BINOL

2024

Chem. Rev.

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“…图式 47 铑催化螺硅杂双环丁烷的不对称开环扩环反应 Scheme 47 Rhodium-catalyzed asymmetric ring expansion reaction of spirosilabicyclobutanes 近期, 该题组 [56] 开发了一种铑催化螺硅芴与末端炔烃的不对称开环扩环反应, 合成多种具有优异对映选择性的手性 6-/5-硅螺烷骨架手性化合物(Scheme 48). 研究表明, 前手性的硅芴环分子中芳基的邻位取代基对于四元环中 Si-C 键的高效对映选择性断裂至关重要.…”

Section: 分子内 C-h 硅烷化反应unclassified

Research Progress on New Catalytic Reaction Systems for Asymmetric Synthesis of Silicon-Stereogenic Center Containing Compounds

Zeng,

2023

Chinese Journal of Organic Chemistry

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In the past two decades, organosilicon compounds bearing silicon-stereogenic centers have attracted extensive attention in the fields of organic synthesis, materials, and drug design. However, the expansion of organosilicon compounds in these fields has been greatly restricted by limited source of organosilicon compounds. Therefore, the development of highly efficient and selective asymmetric catalytic methods to obtain chiral organosilicon compounds with silicon-stereogenic centers is a challenging task that needs to be solved urgently. The latest research progress on new catalytic reaction systems for asymmetric synthesis of silicon-stereogenic center containing organosilanes since 2011 is mainly summarized.

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“…Among the synthetic methodologies developed, classical electrophilic silylations using a stoichiometric amount of reactive silicon electrophiles, such as TMSOTf or TMSCl, are still a challenging task in fine chemistry as a result of the potential metallic salt byproduct formation . Alternatively, a ring expansion strategy to synthesize six-membered silacycles with highly reactive silacyclobutanes with unsaturated carbon–carbon bonds was recently well-developed by the groups of Song, Zhao, Xu, and Hayashi but needs a pre-installed silicon reagent (Scheme b). On the other hand, direct C–H bond silylation has attracted attention as a competitive alternative process to access organosilicon compounds owing to their atom and step economies …”

mentioning

confidence: 99%

Ruthenium-Catalyzed Sequential Hydrosilylation/Dehydrogenation and C–H Silylation: Synthesis of Six-Membered Indole Silacycles and Pyrrole Silyl Ether Cycles

Li,

Xu,

Liang

et al. 2024

Org. Lett.

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Selective dehydrogenative C−H silylation is one of the most powerful tools to synthesize silacycles. Herein, we developed Ru-catalyzed sequential hydrosilylation/C−H silylation of allyl-indoles and dehydrogenative O−H/C−H silylation of pyrrole phenols. Both six-membered indole silacycles and pyrrole silyl ether cycles were successfully synthesized with good functional group tolerance. Furthermore, the RuHCl(CO)(PPh 3 ) 3 catalyst exhibited high reaction compatibility in hydrosilylation of alkene, dehydrogenative O−H silylation, and C−H silylation.

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Enantioselective Synthesis of 6/5-Spirosilafluorenes by Asymmetric Ring Expansion of 4/5-Spirosilafluorenes with Alkynes

Cited by 16 publications

References 41 publications

Regioselective Substitution of BINOL

Regioselective Substitution of BINOL

Research Progress on New Catalytic Reaction Systems for Asymmetric Synthesis of Silicon-Stereogenic Center Containing Compounds

Ruthenium-Catalyzed Sequential Hydrosilylation/Dehydrogenation and C–H Silylation: Synthesis of Six-Membered Indole Silacycles and Pyrrole Silyl Ether Cycles

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