36872-11-4Relevant academic research and scientific papers
Highly Selective and Catalytic Generation of Acyclic Quaternary Carbon Stereocenters via Functionalization of 1,3-Dienes with CO2
Chen, Xiao-Wang,Zhu, Lei,Gui, Yong-Yuan,Jing, Ke,Jiang, Yuan-Xu,Bo, Zhi-Yu,Lan, Yu,Li, Jing,Yu, Da-Gang
, p. 18825 - 18835 (2019/11/28)
The catalytic asymmetric functionalization of readily available 1,3-dienes is highly important, but current examples are mostly limited to the construction of tertiary chiral centers. The asymmetric generation of acyclic products containing all-carbon quaternary stereocenters from substituted 1,3-dienes represents a more challenging, but highly desirable, synthetic process for which there are very few examples. Herein, we report the highly selective copper-catalyzed generation of chiral all-carbon acyclic quaternary stereocenters via functionalization of 1,3-dienes with CO2. A variety of readily available 1,1-disubstituted 1,3-dienes, as well as a 1,3,5-triene, undergo reductive hydroxymethylation with high chemo-, regio-, E/Z-, and enantioselectivities. The reported method features good functional group tolerance, is readily scaled up to at least 5 mmol of starting diene, and generates chiral products that are useful building blocks for further derivatization. Systemic mechanistic investigations using density functional theory calculations were performed and provided the first theoretical investigation for an asymmetric transformation involving CO2. These computational results indicate that the 1,2-hydrocupration of 1,3-diene proceeds with high π-facial selectivity to generate an (S)-allylcopper intermediate, which further induces the chirality of the quaternary carbon center in the final product. The 1,4-addition of an internal allylcopper complex, which differs from previous reports involving terminal allylmetallic intermediates, to CO2 kinetically determines the E/Z- and regioselectivity. The rapid reduction of a copper carboxylate intermediate to the corresponding silyl-ether in the presence of Me(MeO)2SiH provides the exergonic impetus and leads to chemoselective hydroxymethylation rather than carboxylation. These results provide new insights for guiding further development of asymmetric C-C bond formations with CO2
Rh-Catalyzed Asymmetric Hydrogenation of β-Branched Enol Esters for the Synthesis of β-Chiral Primary Alcohols
Liu, Chong,Yuan, Jing,Zhang, Jian,Wang, Zhihui,Zhang, Zhenfeng,Zhang, Wanbin
, p. 108 - 111 (2018/01/17)
An asymmetric hydrogenation of β-branched enol esters has been developed for the first time, providing a new route for the synthesis of β-chiral primary alcohols. Using a (S)-SKP-Rh complex bearing a large bite angle and enol ester substrates possessing an O-fomyl directing group, the desired products were obtained in quantitative yields and with excellent enantioselectivities.
Asymmetric Traceless Petasis Borono-Mannich Reactions of Enals: Reductive Transposition of Allylic Diazenes
Jiang, Yao,Thomson, Regan J.,Schaus, Scott E.
, p. 16631 - 16635 (2017/12/13)
The traceless Petasis borono-Mannich reaction of enals, sulfonylhydrazines, and allylboronates, catalyzed by chiral biphenols, results in an asymmetric reductive transposition of the in situ generated allylic diazene. Acyclic 1,4-diene products bearing either alkyl- or aryl-substituted benzylic stereocenters are afforded in excellent yields and enantiomeric ratios of up to 99:1. The use of crotylboronates in the reaction results in concomitant formation of two stereocenters in either a 1,4-syn or anti relationship from the corresponding E- or Z-crotylboronate used in the reaction. The use of β-monosubstituted enals in the asymmetric traceless Petasis borono-Mannich reaction of crotylboronates installs tertiary methyl-bearing stereocenters in good yields and high enantioselectivities.
A Bio-Inspired, Catalytic e → Z Isomerization of Activated Olefins
Metternich, Jan B.,Gilmour, Ryan
, p. 11254 - 11257 (2015/09/21)
Herein, Natures flavin-mediated activation of complex (poly)enes has been translated to a small molecule paradigm culminating in a highly (Z)-selective, catalytic isomerization of activated olefins using (-)-riboflavin (up to 99:1 Z/E). In contrast to the prominent Z → E isomerization of the natural system, it was possible to invert the directionality of the isomerization (E → Z) by simultaneously truncating the retinal scaffold, and introducing a third olefin substituent to augment A1,3-strain upon isomerization. Consequently, conjugation is reduced in the product chromophore leading to a substrate/product combination with discrete photophysical signatures. The operationally simple isomerization protocol has been applied to a variety of enone-derived substrates and showcased in the preparation of the medically relevant 4-substituted coumarin scaffold. A correlation of sensitizer triplet energy (ET) and reaction efficiency, together with the study of additive effects and mechanistic probes, is consistent with a triplet energy transfer mechanism.
An SN2′ displacement approach to allenyl acetates
Asikainen, Martta,Lewis, William,Blake, Alexander J.,Woodward, Simon
supporting information; experimental part, p. 6454 - 6456 (2011/01/03)
Reaction of cuprates derived from R3MgBr/CuI/LiBr (R3 = n-alkyl) with R1CCCH(O2CR2)2 (R1 = sp2 hybridised substituent, R2 = mainly Me, alkyl, Ph) provides access to allenyl esters R1R 3CCCH(O2CR2) (51-88%). Such species are not accessible via rearrangement of precursor propargylic R1R 3C(O2CR2)CCH.
