165072-42-4Relevant articles and documents
Substituent effect on the solvolysis of 2,2-dimethylindan-1-yl chlorides
Fujio, Mizue,Nakata, Kazuhide,Tsuji, Yutaka,Otsu, Toshiaki,Tsuno, Yuho
, p. 321 - 324 (1992)
The substituent effect on the solvolysis of 2,2-dimethylindan-1-yl chlorides was analyzed in terms of the LArSR Eq., to give ρ=-5.81 and R=1.14. The coplanarity of α-t-butylbenzyl cation system was discussed.
The role of stereoelectronic effects on the side-chain fragmentation of alkylaromatic radical cations. The reactivity of 5-methoxy-2,2-dimethylindan-1-ol radical cation
Bellanova, Monica,Bietti, Massimo,Ercolani, Gianfranco,Salamone, Michela
, p. 5039 - 5044 (2002)
A kinetic and products study of the reaction of 2,2-dimethyl-5-methoxyindan-1-ol (1) radical cation, in acidic aqueous solution (pH≤4) has been carried out. 1·+ undergoes C-H deprotonation as the exclusive reaction with k=4.6×104s-1. The kinetic data have been compared with those obtained for the radical cations of 1-(4-methoxyphenyl)ethanol (2) and 1-(4-methoxyphenyl)-2,2-dimethyl-1-propanol (3), suggesting that the deprotonation rate increases when the C-H bond is forced into a conformation where it is almost aligned with the π-system. The conclusion that overlap between the scissile bond and the π-system is an important requisite for the occurrence of bond cleavage is also supported by the results of DFT calculations carried out for 1·+ and 3·+.
Enantioselective Synthesis of Indanes with a Quaternary Stereocenter via Diastereoselective C(sp3)-H Functionalization
Chen, Jun,Shi, Zhan,Lu, Ping
supporting information, p. 7359 - 7363 (2021/10/01)
A practical synthesis of enantioenriched indane derivatives with quaternary stereocenters was developed via sequential enantioselective reduction and C-H functionalization. Good to excellent enantioselectivity could be achieved by either the CuH-catalyzed asymmetric reduction or the Corey-Bakshi-Shibata (CBS) reduction of indanone derivatives. The subsequent diastereospecific and regioselective rhodium-catalyzed silylation of the methyl C-H bond led to indane derivatives with quaternary centers. This strategy was further applied in syntheses of (nor)illudalane and botryane sesquiterpenoids.
Silylative Kinetic Resolution of Racemic 2,2-Dialkyl 5- and 6-Membered Cyclic Benzylic Alcohol Derivatives Catalyzed by Chiral Guanidine, (R)-N-Methylbenzoguanidine
Yoshimatsu, Shuhei,Nakata, Kenya
supporting information, p. 4679 - 4684 (2019/09/16)
Efficient silylative kinetic resolution of racemic 2,2-dialkyl 5- and 6-membered cyclic benzylic alcohols was achieved using diphenylmethylchlorosilane (Ph2MeSiCl) or phenyldimethylchlorosilane (PhMe2SiCl) as a silyl source catalyzed by chiral guanidine. The reaction could be applied to a broad range of 2,2-dialkyl 1-indanols with good s-values, irrespective of the electronic nature of the substituent on the aromatic ring of the substrates and the type of substituent at the C2-position. In addition, several 2,2-dimethyl 6-membered cyclic and heterocyclic alcohols could be adopted in the reaction. (Figure presented.).
The Photochemistry of Conformationally Rigid Benzylic Esters: 2,2-Dimethyl-1-indanyl Acetates and Pivalates
Pincock, J. A.,Wedge, P. J.
, p. 4067 - 4076 (2007/10/02)
The photochemistry, in methanol, of substituted 2,2-dimethyl-1-indanyl acetates 9a-c and pivalates 10a-c has been studied.In agreement with previous studies on benzylic esters, the results show that the substituents change the yield of products derived from the ion pair.The mechanistic conclusion reached is that the substituents change the oxidation potential of the indanyl radicals and thus the rate constant of electron transfer for converting the radical pair to the ion pair.The results also reveal two other substituent effects.First, substituents can increase the overall efficiency of the photoreaction by enhancing homolytic cleavage.The second effect is conformational.In compounds where the bond that is cleaving is conformationally mobile, such as the C-O bond in benzylic esters, substituents on the ring can change the population of the reactive conformer and thus the overall efficiency of the reaction.For the indanyl acetate esters, the difference in excited-state reaction rate between the m- and p-methoxy substituted ester is 15:1.For the m- and p-methoxy substituted benzyl acetates, this difference in reaction rate is 48:1.The larger difference in reaction rate for the conformationally mobile benzylic esters is attributed to a higher population of the unreactive conformer for the p-methoxy substituted ester.
