With suitable conditions in hand, the scope of aromatic alkenes was firstly examined with PhMe2SiBpin as the boron source and 4-cyanopyridine as the other coupling partner (Table ). The initially tested aryl alkenes represent an extensive sampling of both simple styrene and 1,1/1,2-disubstituted olefins with electron-rich or electron-deficient substituents. Substituted styrenes underwent silylarylation effectively with good to excellent yields (5-9, 11, and 12), except for one instance in which a strong electron-withdrawing CF3 group was installed at the para position of the C=C bond (10). Furthermore, we found that 1,1-disubstituted alkenes readily undergo addition reactions to give the difunctionalization products bearing quaternary carbon centers in good yields (14-26, 65%-94%), including three examples with highly crowded triaryl quaternary carbon centers (24-26). These results clearly illustrate the unique features of this method compared to transition-metal-catalyzed difunctionalizations , in which the formation of the quaternary carbon center remains a great challenge . Surprisingly, a series of substituents, such as boronic After establishing that a wide array of aromatic alkenes is applicable to this transformation, we turned our attention to the scope of electrophiles with different types of leaving groups. As exemplified in Table , the scope is striking because both C(sp 2 )-and C(sp 3 )-hybridized electrophiles, including aryl cyanide, aryl chloride, alkyl chloride, and alkyl bromides, could be employed. Using styrene as the model substrate, we found that most of the cyano-substituted pyridines (33-54) are effective coupling partners, despite the electronic and substituent effects of the cyano group at the C-2, C-3, and C-4 positions. These results clearly illustrate the true complementary nature of this method to Minisci-type reactions or radical-based ipso-substitution of pyridine nitriles given that a challenging C-3 substituted pyridine is also accessible (48). More importantly, other aryl (or azines) cyanides, including 2 or 4-cyanoquinoline, 1-cyano-isoquinoline, 1,4-or 1,2-dicyanobenzene, 4-cyanobiphenyl, and even benzonitrile were also allowed in the reaction, providing the desired products 49-55 in moderate to good yields. Besides, this approach can facilitate access to the 1,2-difunctionalization of alkenes from the abundantly available aryl chloride, alkyl chloride, and alkyl bromides (56-65). For example, the bulky triphenylmethyl chloride was also a suitable coupling partner for the transformation, providing the desired product 57 in 62% yields. Although chlorobenzene (58) did not react under current conditions, chlorinated heterocycles, including 4-chloropyridine, 4-chloroquinoline, 9-chloroacridine and 2chlorobenzothiazole provide the desired products in good yields (4, 49, and 59-62). The alkyl bromides were also suitable coupling partners in the reaction, providing the desired product 63-65 in 58%-89% yields. Given there are plenty of aromatic electrophiles commercially accessible, the reactivity of the different leaving groups was then examined with 2-substituted pyridines. We found that 2-chloro-, bromo-, iodo-and benzenesulfonyl-substituted pyridine are less effective, but 2fluoropyridine, 2-cyanopyridine, 2-methoxylpyridine and 2-methylthiopyridine are viable 2pyridinyl precursors (see Supplementary Table , and the observed reactivities are consistent with DFT calculations shown in Supplementary Table ). Furthermore, this transformation is also applicable to the derivatization of drug-relevant molecules. Three alkenes derived from stugeron, naftifine, and estradiol derivatives could be readily converted to the corresponding products in 51-81% yields (66-68). In addition, this difunctionalization platform enables access to compound libraries of antihistamine pheniramine derivatives from abundantly available aryl cyanides. Using the readily accessible (E)-N,N-dimethyl-3-phenyl-2-propen-1-amine as the substrate, the desired pheniramine analogues 69-71 could be rapidly prepared in 46%-78% yields. It should be noted that both heterocycles and 1,1-diaryl motifs are privilege structures in medicinal chemistry ; therefore, our one-pot, two-bond-forming transformation represents an attractive route to synthesize a wide range of compounds potentially relevant to medicinal applications from readily accessible precursors.