- π-mediated rearrangements and 1,2-H shifts of indanylcarbenes
-
Absolute rate constants determined for 1,2-C and 1,2-H migrations of cyclobutyl-, cyclopentyl-, benzocyclobutenyl- and benzocyclopentenyl-(chloro)- or-(acetoxy)-carbenes reveal that 'phenyl' carbon migrations are preferred to alternative 1,2-C shifts due
- Moss, Robert A.,Ma, Wei,Sauers, Ronald R.
-
-
Read Online
- Asymmetric Deoxygenative Cyanation of Benzyl Alcohols Enabled by Synergistic Photoredox and Copper Catalysis?
-
Summary of main observation and conclusion. An enantioselective deoxygenative cyanation of benzyl alcohols was accomplished for the first time through the synergistic photoredox and copper catalysis. This reaction features the use of organic photosensitizer and low-cost 3d metal catalyst, simple and safe operations, and extremely mild conditions. A variety of chiral benzyl nitriles were produced in generally good yields and high level of enantiocontrols from readily available feedstocks (22 examples, up to 93% yield and 92% ee).
- Chen, Hong-Wei,Lu, Fu-Dong,Cheng, Ying,Jia, Yue,Lu, Liang-Qiu,Xiao, Wen-Jing
-
supporting information
p. 1671 - 1675
(2020/11/03)
-
- A metal-free direct C (sp3)-H cyanation reaction with cyanobenziodoxolones
-
A metal-free protocol of direct C(sp3)-H cyanation with cyanobenziodoxolones functioning as both cyanating reagents and oxidants was developed. Unactivated substrates, such as alkanes, ethers and tertiary amines, were thereby transformed to the corresponding nitriles in moderate to high yields. Mechanistic studies indicated that the cyanation proceeded with two potential pathways, which is highly dependent on the substrates: (1) a free radical case for alkanes and ethers and (2) an oxidative case for tertiary amines.
- Sun, Ming-Xue,Wang, Yao-Feng,Xu, Bao-Hua,Ma, Xin-Qi,Zhang, Suo-Jiang
-
supporting information
p. 1971 - 1975
(2018/03/23)
-
- Copper-Catalyzed Cyanation of N-Tosylhydrazones with Thiocyanate Salt as the "cN" Source
-
A novel protocol for the synthesis of α-aryl nitriles has been successfully achieved via a copper-catalyzed cyanation of N-tosylhydrazones employing thiocyanate as the source of cyanide. The features of this method include a convenient operation, readily available substrates, low-toxicity thiocyanate salts, and a broad substrate scope.
- Huang, Yubing,Yu, Yue,Zhu, Zhongzhi,Zhu, Chuanle,Cen, Jinghe,Li, Xianwei,Wu, Wanqing,Jiang, Huanfeng
-
p. 7621 - 7627
(2017/07/26)
-
- Domino synthesis of fluorine-substituted polycyclic aromatic hydrocarbons: 1,1-difluoroallenes as synthetic platforms
-
Rather crafty: 1,1-Difluoroallenes bearing an aryl group and a cyclopentene moiety undergo indium(III)-catalyzed Friedel-Crafts-type cyclization with subsequent ring expansion and dehydrogenation to afford fluorinated polycyclic aromatic hydrocarbons in high yields. The introduction of an Ar group was effected by in situ halogenation of the intermediary indium species and a subsequent Suzuki-Miyaura reaction. Copyright
- Fuchibe, Kohei,Mayumi, Yuka,Zhao, Nan,Watanabe, Shumpei,Yokota, Misaki,Ichikawa, Junji
-
supporting information
p. 7825 - 7828
(2013/08/23)
-
- Enantioselective nickel-catalyzed hydrocyanation of vinylarenes using chiral phosphine-phosphite ligands and TMS-CN as a source of HCN
-
Anti-headache chemistry: In the presence of a tailored modular P,P ligand the nickel-catalyzed addition of HCN, generated in situ from TMS-CN, to styrene derivatives proceeds with an unprecedented level of stereocontrol (up to 97 % ee) to give 2-aryl-acetonitriles, for example, the depicted precursor of Ibuprofen. Copyright
- Falk, Anna,Goederz, Anna-Lena,Schmalz, Hans-Guenther
-
supporting information
p. 1576 - 1580
(2013/03/13)
-
- Novel 2-imidazoles as potent and selective α1A adrenoceptor partial agonists
-
Novel 2-imidazoles have been identified as potent partial agonists of the α1A adrenergic receptor, with good selectivity over the α1B, α1D and α2A receptor sub-types. Sulfonamide 23 possessed attractive drug-like properties with respect to physicochemical and ADME properties and wide ligand selectivity.
- Whitlock, Gavin A.,Conlon, Kelly,McMurray, Gordon,Roberts, Lee R.,Stobie, Alan,Thurlow, Richard J.
-
p. 2930 - 2934
(2008/12/22)
-
- Mild cobalt-catalyzed hydrocyanation of olefins with tosyl cyanide
-
Mild-mannered and well-behaved: A conceptually new hydrocyanation reaction for non-activated olefins provides secondary and tertiary nitriles in good yields under mild conditions. Salient features of this process include broad functional-group tolerance, readily available starting materials, and ease of execution.
- Gaspar, Boris,Carreira, Erick M.
-
p. 4519 - 4522
(2008/09/17)
-
- INDANE COMPOUNDS AS CCR5 ANTAGONISTS
-
The present invention relates to compounds of formula (I), or pharmaceutically acceptable derivatives thereof, useful in the treatment of CCR5-related diseases and disorders, for example, useful in the inhibition of HIV replication, the prevention or treatment of an HIV infection, and in the treatment of the resulting acquired immune deficiency syndrome (AIDS).
- -
-
-
- Stereoselective synthesis of quaternary benzylic carbons using C2 symmetric imidazolines and tetrahydrofuran as electrophile
-
Alkylative ring opening of tetrahydrofuran in the presence of 9-BBN triflate is studied. Dianions derived from C2 symmetric imidazolines induce excellent to modest acyclic diastereoselectivity to form quaternary benzylic centers, using the 9-BBN triflate/THF system or methyl iodide as electrophiles. The direction of the stereoinduction is consistent in both cases. Absolute configuration for the newly created stereogenic center was established by chemical correlation. Low-temperature NMR studies of the dilithiated intermediates 42 and 43 suggest the presence of N- and C- metalated compounds, where the metal-bearing benzylic carbon is sp3 hybridized.
- Dalko, Peter I.,Langlois, Yves
-
p. 8107 - 8117
(2007/10/03)
-
- Total Synthesis of the Spirans of Cannabis: Cannabispiradienone, Cannabispirenone-A and -B, Cannabispirone, α- and β-Cannabispiranols and the Dihydrophenanthrene Cannithrene-1
-
O-Methylcannabispirenone has been synthesised (57percent overall from 3,5-dimethoxycinnamic acid) via 5,7-dimethoxyindanone, p-tolylsulphonylmethyl isocyanide conversion into the 1-nitrile, alkylation with 1-iodo-3,3-ethylenedioxybutane, deacetalisation, and spirocyclisation. 5,7-Dimethoxyindanone is 7-deprotected by boron trichloride with high selectivity, and re-protected as the methoxyethoxymethyl ether: following the above route, finally deprotecting by boron trichloride, gives cannabispirenone-A (2) in 21percent overall yield.O-Methylcannabispirenone can be demethylated to give (2) by lithium 1,1-dimethylethanethiolate: demethylation with boron tribromide gives cannabispirenone-B (3).Hydrogenation of synthetic cannabispirenone-A gives cannabispirone (4), reduced by borohydride to the epimeric α-(6) and β-(5) cannabispiranols, separated by h.p.l.c.Dehydrogenation of O-methylcannabispirenone with dichlorodicyanobenzoquinone, followed by lithium 1,1-dimethylethanethiolate demethylation, gives cannabispiradienone (1).Under acidic conditions, the latter undergoes dienone-phenol rearrangement to give cannithrene-1 (8), thus completing the total synthesis of the spiro-cannabinoid group of natural products discussed in the preceding paper.The unsubstituted cannabispirenone parent has also been synthesised.
- Crombie, Leslie,Tuchinda, Patoomratana,Powell, Michael J.
-
p. 1477 - 1484
(2007/10/02)
-