1512864-19-5Relevant articles and documents
Silver(I)-Catalyzed Diastereoselective Synthesis of anti-1,2-Hydroxyboronates
Joannou, Matthew V.,Moyer, Brandon S.,Goldfogel, Matthew J.,Meek, Simon J.
, p. 14141 - 14145 (2015)
A catalytic protocol for the diastereoselective synthesis of anti-1,2-hydroxyboronates is described. The process provides access to secondary alkyl organoborons. The deborylative 1,2-addition reactions of alkyl 1,1-diborons proceed in the presence of a silver(I) salt with either KOtBu or nBuLi as an activator. The catalytic diastereoselective protocol can be extended to aryl, alkenyl, and alkyl aldehydes with up to 99:1 d.r.
Electrophilic Fluorination of Alkenes via Bora-Wagner–Meerwein Rearrangement. Access to β-Difluoroalkyl Boronates
Biosca, Maria,Himo, Fahmi,Szabó, Kálmán J.,Wang, Qiang
supporting information, p. 26327 - 26331 (2021/11/16)
The electrophilic fluorination of geminal alkyl substituted vinyl-Bmida derivatives proceeds via bora-Wagner–Meerwein rearrangement. According to DFT modelling studies this rearrangement occurs with a low activation barrier via a bora-cyclopropane shaped TS. The Bmida group has a larger migration aptitude than the alkyl moiety in the Wagner–Meerwein rearrangement of the presented electrophilic fluorination reactions.
Copper-Catalyzed Borylative Methylation of Alkyl Iodides with CO as the C1 Source: Advantaged by Faster Reaction of CuH over CuBpin
Wu, Fu-Peng,Wu, Xiao-Feng
supporting information, p. 11730 - 11734 (2021/04/22)
CuH and CuBpin are versatile catalysts and intermediates in organic chemistry. However, studies that involve both CuH and CuBpin in the same reaction is still rarely reported due to their high reactivity. Now, a study on CuH- and CuBpin-catalyzed borylative methylation of alkyl iodides with CO as the C1 source is reported. Various one carbon prolongated alkyl boranes (RCH2Bpin and RCH(Bpin)2) were produced in moderate to good yields from the corresponding alkyl iodides (RI). In this cooperative system, CuH reacts with alkyl iodide faster than CuBpin.
Zirconium-Catalyzed Atom-Economical Synthesis of 1,1-Diborylalkanes from Terminal and Internal Alkenes
Cui, Xin,Jiao, Haijun,Li, Sida,Wang, Xianjin,Wang, Yue,Wu, Lipeng,Xia, Chungu
supporting information, p. 13608 - 13612 (2020/06/02)
A general and atom-economical synthesis of 1,1-diborylalkanes from alkenes and a borane without the need for an additional H2 acceptor is reported for the first time. The key to our success is the use of an earth-abundant zirconium-based catalyst, which allows a balance of self-contradictory reactivities (dehydrogenative boration and hydroboration) to be achieved. Our method avoids using an excess amount of another alkene as an H2 acceptor, which was required in other reported systems. Furthermore, substrates such as simple long-chain aliphatic alkenes that did not react before also underwent 1,1-diboration in our system. Significantly, the unprecedented 1,1-diboration of internal alkenes enabled the preparation of 1,1-diborylalkanes.
Boryl-Directed, Ir-Catalyzed C(sp3)-H Borylation of Alkylboronic Acids Leading to Site-Selective Synthesis of Polyborylalkanes
Yamamoto, Takeshi,Ishibashi, Aoi,Suginome, Michinori
supporting information, p. 6235 - 6240 (2019/08/26)
Pyrazolylaniline serves as a temporary directing group attached to the boron atom of alkylboronic acids in Ir-catalyzed C(sp3)-H borylation. The reaction takes place at α-, β-, and γ-C-H bonds, giving polyborylated products including di-, tri-, tetra-, and even pentaborylalkanes. α-C-H borylation was generally found to be the preferred reaction of primary alkylboronic acid derivatives, whereas β- or γ-borylation also occurred if β- or γ-C-H bonds were located on the methyl group.
Preparation method and application of geminal diboron compound
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Paragraph 0040; 0041; 0042; 0044; 0045; 0046, (2019/05/22)
The invention discloses a preparation method and application of a geminal diboron compound. The preparation method includes: in a protective atmosphere, subjecting a uniform mixture system of a carbonyl compound, a diboron reagent, an iron catalyst, an alkaline substance, a proton source and a solvent to reaction at 60-150 DEG C for 3-36 h, and separating to obtain the geminal diboron compound. The preparation method herein constructs, in one step, the geminal diboron compound which is difficult to efficiently implement in the past, from simple, economical and easily accessible materials as substrates under catalyst of the iron catalyst; the geminal diboron compound has a good application prospect in the sciences of pharmaceutical synthetic intermediates and organic photoelectric materials; the preparation method herein helps solve the problem that the field of traditional preparation of geminal diboron compounds requires pre-functionalization or some substrates are incompatible; the reaction conditions are relatively mild; operation is simple; the raw materials are economical and easy to attain; the reaction efficiency is high; the preparation method herein provides good functional group compatibility.
C-O Functionalization of α-Oxyboronates: A Deoxygenative gem-Diborylation and gem-Silylborylation of Aldehydes and Ketones
Wang, Lu,Zhang, Tao,Sun, Wei,He, Zeyu,Xia, Chungu,Lan, Yu,Liu, Chao
, p. 5257 - 5264 (2017/05/04)
A deoxygenative gem-diborylation and gem-silylborylation of aldehydes and ketones is described. The key for the success of this transformation is the base-promoted C-O bond borylation or silylation of the generated α-oxyboronates. Experimental and theoret
Synthesis of vinyl boronates from aldehydes by a practical boron-Wittig reaction
Coombs, John R.,Zhang, Liang,Morken, James P.
supporting information, p. 1708 - 1711 (2015/04/14)
A highly stereoselective boron-Wittig reaction between stable and readily accessible 1,1-bis(pinacolboronates) and aldehydes furnishes a variety of synthetically useful di- and trisubstituted vinyl boronate esters.
Simple access to elusive α-boryl carbanions and their alkylation: An umpolung construction for organic synthesis
Hong, Kai,Liu, Xun,Morken, James P.
supporting information, p. 10581 - 10584 (2014/08/18)
The reaction of 1,1-bis(pinacolboronate) esters with alkyl halides can be effected by metal alkoxides and provides a strategy for the construction of organoboronate compounds. The reaction is found to occur by alkoxide-induced deborylation and generation of a boron-stabilized carbanion.
Palladium(0)-catalyzed cross-coupling of 1,1-diboronates with vinyl bromides and 1,1-dibromoalkenes
Li, Huan,Zhang, Zhikun,Shangguan, Xianghang,Huang, Shan,Chen, Jun,Zhang, Yan,Wang, Jianbo
supporting information, p. 11921 - 11925 (2015/01/09)
Palladium-catalyzed cross-coupling reactions of 1,1-diboronates with vinyl bromides and dibromoalkenes were found to afford 1,4-dienes and allenes, respectively. These reactions utilize the high reactivities of both 1,1-diboronates and allylboron intermediates generated in the initial coupling.
