Testing the functional tolerance of the Piers–Rubinsztajn reaction: a new strategy for functional silicones

Abstract

The Piers-Rubinsztajn reaction, involving B(C(6)F(5))(3)-catalyzed siloxane formation from hydrosilanes + alkoxysilanes, is tolerant of a wide variety of functional groups, and provides a generic strategy for the preparation of structurally complex functional silicones.

Siloxane‐Bond Formation Promoted by Lewis Acids: A Nonhydrolytic Sol–Gel Process and the Piers–Rubinsztajn Reaction

“…[42] Amines are a strong enough Lewis base to complex and deactivate B(C 6 F 5 ) 3 . [42] Amines are a strong enough Lewis base to complex and deactivate B(C 6 F 5 ) 3 .…”

“…Siloxane for-mation proceeds preferentially with tert-butoxy and diphenylmethoxy groups rather than methoxy and ethoxy groups. [42,44,69] By using the Piers-Rubinsztajn reaction, a new type of silicone surfactant was also synthesized. [16] The procedure described here can be applied for the synthesis of various alkoxysiloxane oligomers, namely, Si[OSiR 1 (OR 2 ) 2 ] 4 (R 1 = H, Me, ÀCH=CH 2 , Ph, nBu, À(CH 2 ) 3 Cl; R 2 = Me, Et) and (MeO) 4Àn Si[OSiR 1 (OR 2 ) 2 ] n (n = 1, 2).…”

Extension of the Application of Piers‐Rubinsztajn Conditions to Produce Triarylamine Pendant Dimethylsiloxane Copolymers

“…The accepted mechanism for reaction is illustrated in Figure 3 for a “D*” § unit of methylhydrosiloxane. Although triarylamines are Lewis basic and can interact with BCF,28 we have found triarylamines have sufficient steric hindrance and are sufficiently weak as Lewis bases that they do not fully quench BCF's activity and therefore triarylamine ethers can be used to functionalize siloxanes using mild conditions as in Figure 1 2a…”

Synthesis of polyesters containing disiloxane subunits: Structural characterization, kinetics, and an examination of the thermal tolerance of Novozym-435

“…Other general cure methods include high temperature vulcanizations, and thermal-or coppermediated [1,3]-dipolar additions [5,6]. More recent work on the Piers-Rubensztajn reaction has lead to the development of B(C 6 F 5 ) 3 as a catalyst for the preparation of star-shaped siloxanes and functionalized silicones from hydrosilanes and alkoxysilanes [7][8][9].…”