A Relay Strategy Actuates Pre-Existing Trisubstituted Olefins in Monoterpenoids to Form New Trisubstituted Olefins by Cross Metathesis

<b><u>Abstract:</u></b> A retrosynthetic disconnection-reconnection analysis of epoxypolyenes – substrates that can undergo cyclization to podocarpane-type tricycles – reveals relay-actuated Δ^6,7-functionalized monoterpenoid alcohols for ruthenium benzylidene catalyzed olefin cross metathesis with homoprenyl benzenes. Successful implementation of this approach provided several epoxypolyenes as expected (<i>E</i>:<i>Z</i>, ca. 2-3:1). The method is further generalized for the cross metathesis of pre-existing trisubstituted olefins in other relay-actuated Δ^6,7-functionalized monoterpenoid alcohols with various other trisubstituted alkenes to form new trisubstituted olefins. Epoxypolyene cyclization of an enantiomerically pure, but geometrically impure, epoxypolyene substrate provides an enantiomerically pure, trans-fused, podocarpane-type tricycle (from the <i>E</i>-geometrical isomer).<br>

A Relay Strategy Actuates Pre-Existing Trisubstituted Olefins in Monoterpenoids to Form New Trisubstituted Olefins by Cross Metathesis

<b><u>Abstract:</u></b> A retrosynthetic disconnection-reconnection analysis of epoxypolyenes – substrates that can undergo cyclization to podocarpane-type tricycles – reveals relay-actuated Δ^6,7-functionalized monoterpenoid alcohols for ruthenium benzylidene catalyzed olefin cross metathesis with homoprenyl benzenes. Successful implementation of this approach provided several epoxypolyenes as expected (<i>E</i>:<i>Z</i>, ca. 2-3:1). The method is further generalized for the cross metathesis of pre-existing trisubstituted olefins in other relay-actuated Δ^6,7-functionalized monoterpenoid alcohols with various other trisubstituted alkenes to form new trisubstituted olefins. Epoxypolyene cyclization of an enantiomerically pure, but geometrically impure, epoxypolyene substrate provides an enantiomerically pure, trans-fused, podocarpane-type tricycle (from the <i>E</i>-geometrical isomer).<br>

Currierite, Na4Ca3MgAl4(AsO3OH)12·9H2O, a new acid arsenate with ferrinatrite-like heteropolyhedral chains from the Torrecillas mine, Iquique Province, Chile

The new mineral currierite (IMA2016-030), Na4Ca3MgAl4(AsO3OH)12·9H2O, was found at the Torrecillas mine, Iquique Province, Chile, where it occurs as a secondary alteration phase in association with anhydrite, canutite, chudobaite, halite, lavendulan, magnesiokoritnigite, quartz, scorodite and torrecillasite. Currierite occurs as hexagonal prisms, needles and hair-like fibres up to ∼200 μm long, in sprays. The crystal forms are ﹛100﹜ and ﹛001﹜. Crystals are transparent, with vitreous to silky lustre and white streak. The Mohs hardness is ∼2, tenacity is brittle, but elastic in very thin fibres, and the fracture is irregular. Crystals exhibit at least one good cleavage parallel [001]. The measured density is 3.08(2) g cm -3 and the calculated density is 3.005 g cm -3. Optically, currierite is uniaxial (–) with ω= 1.614(1) and ε= 1.613(1) (measured in white light). The mineral is slowly soluble in dilute HCl at room temperature. The empirical formula, determined from electron-microprobe analyses, is (Na3.95A12.96Ca2.74Mg1.28Fe0.633+Cu0.13K0.08Co0.03Σ11.80 (AS11.685+Sb0.325+Σ12(O56.96Cl0.04)Σ57H30.81. Currierite is hexagonal, P622, with a = 12.2057(9), c = 9.2052(7) Å, V= 1187.7(2) Å3 and Z = 1. The eight strongest powder X-ray diffraction lines are [dobs Å(I)(hkl)]: 10.63(100)(100), 6.12(20)(110), 5.30(15)(200), 4.61(24)(002), 4.002(35)(210), 3.474(29)(202), 3.021(96)(212) and 1.5227(29)(440,334,612). The structure of currierite (R1 = 2.27% for 658 Fo > 4σF reflections) is based upon a heteropolyhedral chain along c in which AlO6 octahedra are triple-linked by sharing corners with AsO3OH tetrahedra. Chains are linked to one another by bonds to 8(4 + 4)-coordinated Na and 8-coordinated Ca forming a three-dimensional framework with large cavities that contain rotationally disordered Mg(H2O)6 octahedra. The chain in the structure of currierite is identical to that in kaatialaite and a geometrical isomer of that in ferrinatrite. The mineral is named in honour of Mr. Rock Henry Currier (1940–2015), American mineral dealer, collector, author and lecturer.

Oxatriquinane Derivatives: A Theoretical Investigation of SN1-SN2 Reactions Borderline

This study investigated the nucleophilic substitution reaction mechanisms of 5 oxatriquinane derivatives, namely: oxatriquinane (OTQ), 1,4,7-trimethyloxatriquinane (TMO), 1,4,7-triethyloxatriquinane (TEO), 1,4,7-tri-iso-propyloxatriquinane (TIO) and 1,4,7-tri-tert-butyloxatriquinane (TTO). In addition to the G3 conformation (one with the substituent groups at 1,4 and 7 positions pointing into the plane of the paper) originally proposed by the previous workers, Mascal et al. in 2008 and Gunbas et al. in 2013, one more geometrical isomer was considered again for each of the derivatives, the 2G1 isomer (one in which only 2 of the 3 substituent groups at 1,4 and 7 positions are into the paper plane). Geometry optimization and determination of transition state properties of the conformers corresponding to each molecule (in the presence of azide ion, N3-) provided theoretical evidences on the possible reaction mechanisms. The 2G1 conformer for TTO was found to be unstable. The reactions of OTQ, TMO and TEO with azide ion (N3-) followed SN2 pathway, with SN1mechanism completely lacking. This finding is in agreement with the first set of reports published on this subject in 2008 and 2010 by Mascal’s group. For TIO (in the presence of azide ion), only the presence of SN1 mechanism could be proved without any observation of transition state (TS), even though, it possesses a 2G1 conformer. TTO surprisingly, showed marked evidence of SN1 mechanism also without any evidence of TS. The results obtained showed that OTQ derivatives up to TEO undergo nucleophilic substitution predominantly via SN2, and above which (i.e. for TIO and TTO) the mechanisms predominantly become SN1.

Three closely related thienyl-substituted 1,4-epoxynaphtho[1,2-b]azepines: hydrogen-bonded assembly in one, two and three dimensions

(2R,4S)-2-(3-Methylthiophen-2-yl)-2,3,4,5-tetrahydro-1,4-epoxynaphtho[1,2-b]azepine, C19H17NOS, (I), crystallizes with a single enantiomer in each crystal, whereas its geometrical isomer (2RS,4SR)-2-(5-methylthiophen-2-yl)-2,3,4,5-tetrahydro-1,4-epoxy-naphtho[1,2-b]azepine, (II), and (2RS,4SR)-2-(5-bromothiophen-2-yl)-2,3,4,5-tetrahydro-1,4-epoxynaphtho[1,2-b]azepine, C18H14BrNOS, (III), both crystallize as racemic mixtures. A combination of one C—H...O hydrogen bond and two C—H...π(arene) hydrogen bonds links the molecules of (I) into a three-dimensional framework; the molecules of (II) are linked into aC(4)C(4)[R22(7)] chain of rings by a combination of C—H...N and C—H...O hydrogen bonds; and in (III), whereZ′ = 2, a combination of four C—H...π(arene) hydrogen bonds and two C—H...π(thienyl) hydrogen bonds links the molecules into complex sheets. Comparisons are made with the assembly patterns in some aryl-substituted 1,4-epoxynaphtho[1,2-b]azepines.