Grubbs III

HATU, HOAt, DIEA, CH2CI2 O Grubbs III cat. toluene... 

The present review intends to cover the work reported on nonlinear optics at liquid-liquid interface since the first report of S. G. Grubb et al. [18]. The theoretical aspects of nonlinear optics are first introduced in Section II. The experimental results covering the molecular structure of liquid interfaces are presented in Section III, followed by a section devoted to the dynamics and the reactivity at these interfaces. Section V focuses on new aspects where spherical interfaces with radii of curvature of the order of the wavelength of light are investigated. Section VI presents the field of SFG. 

Reagents (i) H2C=CHCF2Br, In, DMF, sonication, rt (ii) allyl bromide, NaOH, CH2CI2, BU4NHSO4, rt (iii) 5 mol% Grubbs catalyst, CH2CI2, rt... 

Reagents (i) benzyloxy allene, 5 mol% Pd(OAc)2, dppp, Et3N, MeCN (ii) Grubbs catalyst, CH2CI2, rt (iii) BF3.OEt2, CH2CI2, 0 °C then nucleophile (R2). 

Grubbs and co-workers have further investigated the influence of allylic substitution on E/Z diastereocontrol in olefin CM reactions using catalyst 5. In some cases, it was found that secondary and tertiary allylic alcohols could afford complete -selectivity, particularly when a cross-partner bearing allylic heteroatom substitution was used. Also, in contrast to the less reactive catalyst 2, catalyst 5 was found to promote the CM reaction of olefins bearing quaternary allylic substitution (Scheme 7). The cross-partners in these examples represent type III olefins with respect to 5 therefore, they can be applied either stoichiometrically or in excess without a reduction in yield. E/Z ratios of >20 1 were typically observed. 

Two tandem alkene metathesis-oxidation procedures using Grubb s second-generation ruthenium catalyst resulted in unique functional group transformations. Use of sodium periodate and cerium(III) chloride, in acetonitrile-water, furnished cis-diols. Oxidation with Oxone, in the presence of sodium hydrogencarbonate, yielded a-hydroxy ketones.296 Secondary alcohols are oxidized to ketones by a hydrogen... 

Oxathiin 2,2-dioxides (sultones) (e.g., 150) are obtained by the addition of sulfur trioxide to dienes or by ringclosing metathesis (RCM) of sulfonates using the second-generation Grubbs ruthenium catalyst (Scheme 75) . The same catalyst was also successfully employed in the RCM of diallyl disulfide 151 which led quantitatively to 3,6-dihydro-l,2-dithiin 152 (Scheme 76) <20020L1767>. 

Classical ring closures (of the FriedelCrafts, Dieckmann, etc., types) can be applied to benzazepine synthesis <1974AHC(17)45>. Particularly useful are approaches to benzazepines based on transition metal-catalyzed cyclizations , as illustrated by the synthesis of 1-benzazepine derivative 149 in high yield by Ru-catalyzed ring-closing metathesis with Grubbs I catalyst (Scheme 87) <2005JOC1545>. 

Dihydropyrrolizine 16 was obtained from 15 by ring-closing metathesis using commercial first generation Grubbs catalyst (Scheme 10) <2002TL4765, CHEC-III(11.01.7.2)21>. 

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