24329-96-2Relevant academic research and scientific papers
Merging Halogen-Atom Transfer (XAT) and Copper Catalysis for the Modular Suzuki-Miyaura-Type Cross-Coupling of Alkyl Iodides and Organoborons
Zhang, Zhenhua,Górski, Bartosz,Leonori, Daniele
supporting information, p. 1986 - 1992 (2022/02/01)
We report here a mechanistically distinct approach to achieve Suzuki-Miyaura-type cross-couplings between alkyl iodides and aryl organoborons. This process requires a copper catalyst but, in contrast with previous approaches based on palladium and nickel
Photochemical Decarboxylative C(sp3)-X Coupling Facilitated by Weak Interaction of N-Heterocyclic Carbene
Chen, Kun-Quan,Wang, Zhi-Xiang,Chen, Xiang-Yu
supporting information, p. 8059 - 8064 (2020/11/02)
While N-hydroxyphthalimide (NHPI) ester has emerged as a powerful reagent as an alkyl radical source for a variety of C-C bond formations, the corresponding C(sp3)-N bond formation is still in its infancy. We demonstrate herein transition-metal-free decarboxylative C(sp3)-X bond formation enabled by the photochemical activity of the NHPI ester-NaI-NHC complex, giving primary C(sp3)-(N)phth, secondary C(sp3)-I, or tertiary C(sp3)-(meta C)phth coupling products. The primary C(sp3)-(N)phth coupling offers convenient access to primary amines.
Nickel-Catalyzed C-Alkylation of Nitroalkanes with Unactivated Alkyl Iodides
Rezazadeh, Sina,Devannah, Vijayarajan,Watson, Donald A.
supporting information, p. 8110 - 8113 (2017/06/28)
Enabled by nickel catalysis, a mild and general catalytic method for C-alkylation of nitroalkanes with unactivated alkyl iodides is described. Compatible with primary, secondary, and tertiary alkyl iodides; and tolerant of a wide range of functional groups, this method allows rapid access to diverse nitroalkanes.
Ni-catalyzed reductive allylation of unactivated alkyl halides with allylic carbonates
Dai, Yijing,Wu, Fan,Zang, Zhenhua,You, Hengzhi,Gong, Hegui
supporting information; experimental part, p. 808 - 812 (2012/02/16)
Game of two electrophiles: Two partially positively charged sp3 carbon atoms can be connected by using a catalytic Ni species in the presence of an environmentally benign Zn reductant, delivering allylated alkanes (see scheme). This unprecedent
Stereoselective benzylic hydroxylation of 2-substituted indanes using toluene dioxygenase as biocatalyst
Bowers, Nigel I.,Boyd, Derek R.,Sharma, Narain D.,Goodrich, Peter A.,Groocock, Melanie R.,Blacker, A. John,Goode, Paul,Dalton, Howard
, p. 1453 - 1461 (2007/10/03)
Indane, 1A, and a series of 2-substituted indane substrates, 1B-1D, 1G, 1I-1L, were found to undergo benzylic monohydroxylation catalysed by toluene dioxygenase, present in the intact cells of Pseudomonas putida UV 4, to yield enantiopure cis-indan-1-ols, 2A-2D, 2G, 2I-2L of the same absolute configuration at C-1 as major bioproducts. Enantiopure trans-indan-1-ols 6B, 6C, and 6G were also obtained as minor metabolites. Evidence of further sequential benzylic hydroxylation (bis-hydroxylation) was found only with substrates 2A, 1C, 1D and 1L to yield the corresponding enantiopure trans-1,3-diols, 3A, 3C, 3D and 3L. Minor enzyme-catalysed processes also observed include benzylic alcohol oxidation to ketones (4A, 5A, 4B, 4L, 5L), ketone reduction to benzylic alcohol 6A, ester hydrolysis to indan-2-ol 1B, and cis-dihydroxylation of indan-1-ol 6A to triol 7. The enantiopurities and absolute configurations of bioproducts have been determined using MTPA ester formation, circular dichroism spectroscopy and stereochemical correlation methods. The contribution of asymmetric oxidation and kinetic resolution to the production of bioproducts of high ee (>98%), and the metabolic sequence involved in their biotransformation by P. putida UV4 is discussed. Enantiocomplementarity was found during the benzylic hydroxylation of indan-2-ol 1B, using toluene dioxygenase and naphthalene dioxygenase, when both single enantiomers of the metabolites 2B, 4B and 6B of opposite configurations were obtained.
2-substituted-(2SR)-2-amino-2-((1SR,2SR)-2-carboxycycloprop-1- yl)glycines as potent and selective antagonists of group II metabotropic glutamate receptors. 1. Effects of alkyl, arylalkyl, and diarylalkyl substitution
Ornstein, Paul L.,Bleisch, Thomas J.,Arnold, M. Brian,Wright, Rebecca A.,Johnson, Bryan G.,Schoepp, Darryle D.
, p. 346 - 357 (2007/10/03)
In this paper, we describe the synthesis of a series of α-substituted analogues of the potent and selective group II metabotropic glutamate receptor (mGluR) agonist (1S,1'S,2'S)-carboxy-cyclopropylglycine (2, L-CCG 1). Incorporation of a substituent on the amino acid carbon converted the agonist 2 into an antagonist. All of the compounds were prepared and tested as a aeries of four isomers, i.e., two racemic diastereomers. We explored alkyl substitution, both normal and terminally branched; phenylalkyl and diphenylalkyl substitution; and a variety of aromatic and carbocyclic surrogates for phenyl. Affinity for group II mGluRs was measured using [3H]glutamic acid (Glu) binding in rat forebrain membranes. Antagonist activity was confirmed for these compounds by measuring their ability to antagonize (1S,3R)-1-aminocyclopentane-1,3-dicarboxylic acid-induced inhibition of forskolin-stimulated cyclic-AMP in RGT cells transfected with human mGluR2 and mGluR3. We found that while alkyl substitution provided no increase in affinity relative to 2, phenylethyl and diphenylethyl substitution, as in 105 and 109, respectively, were quite beneficial. The affinity of 109 was further enhanced when the two aromatic rings were joined by an oxygen or sulfur atom to form the tricyclic xanthylmethyl and thioxanthylmethyl amino acids 113 and 114, respectively. Amino acid 113, with an IC50 of 0.010 μM in the [3H]Glu binding assay, was 52-fold more potent than 2, whose IC50 was 0.47 μM.
Directionality of Proton Transfer in Solutions. Three Systems of Known Angularity
Menger, F. M.,Chow, J. F.,Kaiserman, H.,Vasquez, P. C.
, p. 4996 - 5002 (2007/10/02)
Three compounds were synthesized each possessing rigid carbon frameworks that hold an oxygen base near a mobile C-H proton in well-defined angular and distance relationships: 2-iodo-4-hydroxyindan, endo-5-hydroxybicycloheptan-2-one, and endo-2-hydroxy-exo-6-bromomethylheptane.Effective proton transfer was detected with the second and third compounds but not the first.The data suggest that C-to-O proton transfer with severely bent O/H/C angles (106 deg) is permissible if the O-H distance is less than the sum of the van der Waals radii. "Long distance" catalysis at active sites of enzymes appears unlikely.
