Chemoselective Borane‐Catalyzed Hydroarylation of 1,3‐Dienes with Phenols

A B(C₆F₅)₃‐catalyzed hydroarylation of a series of 1,3‐dienes with various phenols has been established through a combination of theoretical and experimental investigations, affording structurally diverse ortho‐allyl phenols. DFT calculations show that the reaction proceeds through a borane‐promoted protonation/Friedel–Crafts pathway involving a π‐complex of a carbocation–anion contact ion pair. This protocol features simple and mild reaction conditions, broad functional‐group tolerance, and low catalyst loading. The obtained ortho‐allyl phenols could be further converted into flavan derivatives using B(C₆F₅)₃ with good cis diastereoselectivity. Furthermore, this transformation was applied in the late‐stage modification of pharmaceutical compounds.     

新型光纤光栅扭转传感器研究

报道了一种新型光纤光栅扭转传感器的基本原理和传感结构,推导了扭转测量的理论公式,该传感器的扭角与光纤光栅中心波长的变化呈线性关系.在±40°扭角范围内,技术上实现了灵敏度为10.715°/nm的扭转传感.     

Catalytic Dehydrogenation of Ammonia Borane Mediated by a Pt(0)/Borane Frustrated Lewis Pair: Theoretical Design

A new efficient metal-based frustrated Lewis pair constructed by (P^tBu₃)₂Pt and B(C₆F₅)₃ was designed through density functional theory calculations for the catalytic dehydrogenation of ammonia borane (AB). The reaction was composed by the successive dehydrogenation of AB and H₂ liberation, which occurs through the cooperative functions of the Pt(0) center and the B(C₆F₅)₃ moiety. Two equivalents of H₂ were predicted to be liberated from each AB molecule. The generation of the second H2 is the rate-determining step, with a Gibbs energy barrier and reaction energy of 27.4 and 12.8 kcal/mol, respectively.     

Photoredox‐Controlled β‐Regioselective Radical Hydroboration of Activated Alkenes with NHC‐Boranes

In this Communication, we report an unprecedented β‐regioselective radical inverse hydroboration (compared with ionic hydroboration) of α,β‐unsaturated amides with NHC‐BH₃ enabled by photoredox catalysis. Density functional theory (DFT) calculations show that the unique photoredox cycle is a key factor to control the β‐regioselective radical hydroboration, by lowering the energy barrier in comparison with other pathways. This protocol provides a general and convenient route to construct a wide range of structurally diverse β‐borylated amides in synthetically useful yields under mild conditions.     

Linear Quasi-chirp-free Tuning of Fiber Grating with Torsional Beam

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Mechanistic Insight into Hydroboration of Imines from Combined Computational and Experimental Studies

Boron Lewis acid-catalyzed and catalyst-free hydroboration reactions of imines are attractive due to the mild reaction conditions. In this work, the mechanistic details of the hydroboration reactions of two different kinds of imines with pinacolborane (HBpin) are investigated by combining density functional theory calculations and some experimental studies. For the hydroboration reaction of N-(α-methylbenzylidene)aniline catalyzed by tris[3,5-bis(trifluoromethyl)phenyl]borane (BAr^F₃), our calculations show that the reaction proceeds through a boron Lewis acid-promoted hydride transfer mechanism rather than the classical Lewis acid activation mechanism. For the catalyst- and solvent-free hydroboration reaction of imine, N-benzylideneaniline, our calculations and experimental studies indicate that this reaction is difficult to occur under the reaction conditions reported previously. With a combination of computational and experimental studies, we have established that the commercially available BH₃ ⋅ SMe₂ can serve as an efficient catalyst for the hydroboration reactions of N-benzylideneaniline and similar imines. The hydroboration reactions catalyzed by BH₃ ⋅ SMe₂ are most likely to proceed through a hydroboration/B−H/B−N σ-bond metathesis pathway, which is very different from that of the reaction catalyzed by BAr^F₃.     

Borane-catalyzed selective dihydrosilylation of terminal alkynes: reaction development and mechanistic insight

Here, we describe simple B(C₆F₅)₃-catalyzed mono- and dihydrosilylation reactions of terminal alkynes by using a silane-tuned chemoselectivity strategy, affording vinylsilanes and unsymmetrical geminal bis(silanes). This strategy is applicable to the dihydrosilylation of both aliphatic and aryl terminal alkynes with different silane combinations. Gram-scale synthesis and conducting the reaction without the exclusion of air and moisture demonstrate the practicality of this methodology. The synthetic utility of the resulting products was further highlighted by the structural diversification of geminal bis(silanes) through transforming the secondary silane into other silyl groups. Comprehensive theoretical calculations combined with kinetical isotope labeling studies have shown that a prominent kinetic differentiation between the hydrosilylation of alkynes and vinylsilane is responsible for the chemoselective construction of unsymmetrical 1,1-bis(silanes).

A B(C₆F₅)₃/silane-based system enables the chemoselective dihydrosilylation of terminal alkynes. Using a combination of different types of hydrosilanes, a series of unsymmetrical or symmetrical 1,1-bis(silanes) could be constructed.     

Photoredox-Controlled β-Regioselective Radical Hydroboration of Activated Alkenes with NHC-Boranes

In this Communication, we report an unprecedented β-regioselective radical inverse hydroboration (compared with ionic hydroboration) of α,β-unsaturated amides with NHC-BH₃ enabled by photoredox catalysis. Density functional theory (DFT) calculations show that the unique photoredox cycle is a key factor to control the β-regioselective radical hydroboration, by lowering the energy barrier in comparison with other pathways. This protocol provides a general and convenient route to construct a wide range of structurally diverse β-borylated amides in synthetically useful yields under mild conditions.