rt 4'~
`
`Journak
`of The
`Chemical
`~Society
`
`1
`1980
`
`1
`
`CON1038
`
`

`

`\
`
`,. Jo.:.rnal of The Chemical Society, Chemical Communications
`
`Number 1
`
`3 JANUARY 1980
`
`A twice-mohtnly:6ournal containing urgent accounts of important new work in chemistry published
`by The Chemical Society, Burlington House, London W1V OBN.
`
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`The Editor, Chemical Communications,
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`2
`
`

`

`Journal of
`
`·The Chemical Society,
`
`Ch·emical Communications
`
`NUMBER 7/1980
`
`Preparation and Crystal Structure of S1Il+(AsF6)1 containing the Distorted·
`Right Triangular Prismatic Disulphur Tetraiodine(2+) Cation and a
`Disuiphur Unit of Bond Order greater tlian Two
`·
`
`By jACK PASSMORE,* GEORGE SUTHERLAND, TOM WHIDDEN, and PETERS. WHITE*
`(Depaytment of Chemistry, University of New Brunswick, P.O. Box 4400, Fredericton, N.B., Canada E3B 5A3)
`
`The data were corrected for absorption and the structure
`was solved by direct methods. Least-squares refinement,
`with anisotropic thermal parameters for sulphur, iodine,
`and arsenic gave a final R = 0·074, Rw = 0·119.t The
`ions with
`structure consists of discrete S2I,a+ and AsF6-
`weak anion-cation contacts. Attempts
`to refine
`the
`fluorine thermal parameters anisotropically gave exCessively
`high values indicating some rotational disorder of the AsF6-
`units.
`
`/""
`
`5(1)
`
`!(2)
`
`Summayy S2I 42+(AsF6-:-) 2 has been prepared and its crystal
`2+ cation was found
`structure determined 'in which the S2I 4
`to have a distorted right triangular prismatic structure,
`with one S2 and two I 2 units joined by weak sulphur(cid:173)
`iodine bonds; the sulphur-sulphur bond distance is the
`shortest reported in an isolated compound, and is indica(cid:173)
`tive of the presence of a 3p1T-3p1T bond and a bond order
`greater than two.
`
`SuLPHUR iodides, until recently regarded as essentially non(cid:173)
`existent? are proving to be very different from the other
`sulphur halides. 2 The neutral binary sulphur~iodine species
`s.!z has been reported, although it is stable only at low
`tempe.t;atures,3 •' and attempts to prepare SI3+MF6-
`(M =
`As, Sb), analogous to SX3+ (X= F, Cl, Br) 6 led to stable
`salts. 6 •7
`Subsequently,
`S7I+MF6-
`[(S7I) 2I]2+(SbF6-)a·
`2AsF3
`
`8 and (S7I+),S42+(AsF6-) 69 were characterized.
`In an
`(cf. S2F+AsF6-)1° by the
`attempt to prepare S2I+AsF6-
`
`reaction of S42+(AsF6-)28 with an excess of iodine, S2I42+(cid:173)
`(AsF6-)2 was characterized as a product, and then synthe(cid:173)
`sized quantitatively in liquid sulphur dioxide according to
`equation (1).
`
`__!(2')
`5(1 1)~
`
`so.
`!58 + 2I2 + 3AsF5 ---+ S2I,•+(AsF6-)2 + AsF3
`----------!(1')
`(1)
`FIGURE 1. Structure of s.1,H: 5(1)-5(1'), 182·8(1-1); 5(1)-1(1),
`Crystal Data: S2I,2+(AsF6 -).. monoclinic, space group
`285·8(6); 5(1)-1(2), 319·5(6); 1(1)-1(2'), 259·7(2) pm; LI(1)(cid:173)
`S(1)-I(2), 89-5(2); 5(1)-1(1)-1(2'), 87·0(1);
`l(1)-l(2')-S(1'),
`Cdc
`6), a= 965·0(2), b = 1287·4(2), c = 1366·4(4)
`(C211
`78-4(1); 5(1')-5(1)-1(2), 92·9(3); 5(1')-5(1)-1(1),
`101-6(3) 0
`, U = 1694 X 106 pm3 , Z = 4, De =
`pm, ~ = 93·79(2) 0
`Contacts (S-F ~ 320; I-F ~ 335 pm): S(1)-F(5) 303(2); 1(1)(cid:173)
`3·72 g cm-3, p.(Mo-K,,.) = 118·81 cm-1. Data were collected
`F(3), 323(5); 1(1)-F(4), 327(3); 1(2)-F(2), 310(4) pm; non-bonding
`for 28 ~ 50°, 1498 unique reflections, 965 observed (I ~ 2a).
`distance 1(1)-1(2) 426·7(3) pm.
`t The atomic co-ordinates for this work are available on request from Prof. Dr. G. Bergerhoff, Institute fur Anorganische Chemie,
`Universiti!.t, Gerhard-Domagk-Str. 1, D-5300 Bonn 1, West Germany. Any request should be accompanied by the full literature
`citation for this communication.
`
`•
`
`289
`
`3
`
`

`

`318
`
`J.C.S. CHEM. CoMM., 1980 1
`
`numbers in both the solid state and solution with ligands
`that are potentially unidentate.
`We thank the University of Tasmania for a Special
`Research Project Grant and an Honours Scholarship
`(G. H.), the Australian Research· Grants Committee for
`
`financial support, the Australian Development Assistance
`Bureau (N. C.), and Dr. E. E. George for synthesis of
`Etaterpy and di-2-pyridylmethane.
`
`(Received, 17th December 1979; Com. 1310.)
`
`1 See, for example, F. A. Cotton and G. Wilkinson, 'Advanced Inorganic Chemistry,' 3rd edn., Wiley, New York, 1972, p. 524.
`2 D. L. Rabenstein, Accounts Chem. Res., 1978, 11, 100.
`3 See, for example, R. G. Pearson,]. Chem. Educ., 1968, 45, 581; J. E. Huheey, 'Inorganic Chemistry, Principles of Structure and
`Reactivity,' 2nd edn., Harper and Row, New York, 1978, p. 278.
`'
`4 See, for example, G. Y. H. Chu, S. Mansy, R. E. Duncan, and R. S. Tobias, ]. A mer. Chem. Soc., 1978, 100, 593, and references
`therein.
`6 See, for example, U.S. Nandi, J. C. Wang, and N. Davidson, Biochemistry, 1965, 4, 1687.
`6 A.]. Canty and A. Marker, Inorg. Chem., 1976, 15, 425.
`7 A.]. Canty and B. M. Gatehouse, ].C.S. Dalton, 1976, 2018.
`8 A.]. Canty, P. Barron, and P. C. Healy,]. Organometallic Chem., 1979, 179,447.
`9 A.]. Canty, N. Chaichit, B. M. Gatehouse, and A. Marker, Acta Cryst., 1978, B34, 3229.
`1o D. Grdenic, Quart. Rev., 1965, 19, 303.
`11 A.]. Canty, N. Chaichit, and B. M. Gatehouse, Acta Cryst., 1980, B36, in the press.
`10 R. T. C. Brownlee, A.]. Canty, and M. F. Mackay, Austral.]. Chem., 1978, 31, 1933.
`
`Microbiological Synthesis of Optically Active 3-Deuterio-cycloalkanones
`
`By GERARD DAUPHIN, jEAN-CLAUDE GRAMAIN, ALAIN KERGOMARD~, MICHEL F. RENARD, and HENRI VESCHAMBRE
`(E.R.A. 392, Universite de Clermont II, 63170 Aubiere, France)
`
`Summary Optically active 3-deuterio-cyclopentanone and
`3-deuterio-cyclohexanone have been prepared by micro(cid:173)
`biological reduction of 3-deuterio IX~-unsaturated cyclic
`ketones by Beauveria suljurescens.
`
`MANY synthetic problems, in particular the production of an
`asymmetric centre may be solved by use of highly stereo(cid:173)
`specific microbiological reactions. Micro-organisms are
`useful sources of chiral reagents1 and have led, for many
`syntheses, to optical yields of 100%. 2 The synthesis of
`optically active deuterio-cycloalkanones, the optical activity
`of which is due to the presence of deuterium, has been des(cid:173)
`cribed in detail,3-5 Starting from optically active material
`and using classical transformations, deuterium is introduced
`through a stereospecific reaction (reduction of a mesylate
`with LiAlD4). The overall yield of this multi-step trans(cid:173)
`formation is low and the optical purity of the product depends
`on the stereospecificity of the deuterium introduction. The
`optical purity of the products must be checked after each
`step since some of them can lead to partial racemization.
`We have shown• that IX~-ethylenic ketones are reduced to
`saturated ketones with Beauveria suljurescens (ATCC 7159).
`Provided there is an !X-alkyl substituent on the double bond,
`the saturated ketone is optically active and its optical purity
`is equal to 100%. However, cyclic IX~-unsaturated ketones
`having a ~-alkyl substituent are not reduced with B.
`sztlfurescens. Replacement of the a.- or ~-alkyl substituent
`by deuterium should then lead, because of the asymetric
`disturbance by the latter, to optically active cycloal(cid:173)
`kanones.
`Reduction (LiAlD4, then Hp+) of the enol ethers (la) and
`(lb) yields the deuterio-derivatives (2a) and (2b), respec(cid:173)
`tively. t 7 Reduction of (2a) with B. suljurescens, under the
`
`OEt
`
`[CH~0
`
`( 1)
`
`LiAID4
`H
`0 +
`3
`
`0
`
`[CH~D
`.B. suit.
`
`( 2 )·
`
`OH
`
`0
`
`+
`
`QD
`(4)
`
`(CHJAD
`(3)
`
`a; n = 1
`b; n = 2
`
`conditions described elsewhere, 6 is complete within 48 h
`(90% yield) and yields only (5)-( + )-3-deuteriocyclopenta(cid:173)
`none (3a), [1X]~~8 + 2·1 ° (c 0·1 CHC13); c. d., [8Jmax + 62° at
`297 nm (c 8·7 mg/ml, EtOH); 13C n.m.r. (p.p.m. from
`Me4Si) 212·2 (C-1), 38·4 (C-2 + C-5), 23·2 (C-4), and 23·0 [t,
`1J(l3C-2H) 20Hz, C-3].1: This ketone is thus the enantiomer
`of that reported by Djerassi et al. (same optical purity,
`[8Jmax -63o).a
`The similar reduction of (2b) is complete within 96 h
`(85% yield) and yields a 50: 50 mixture (g.l.c.) of (5)-( + )-
`3-deuteriocyclohexanonet
`(3b) and a mixture of the
`stereoisomeric deuteriated alcohols (4), which was separated
`by silica gel column chromatography; (3b): [a.J:~a +2·7°
`(c 0·07, CHC13); c.d. [8Jmax + 122° at 291 nm (c 14 mgjml,
`EtOH); 13C n.m.r. (p.p.m. from Me4Si) 212·1 (C-1), 41·2
`t The isotopic purity of the deuterio compounds is >98% (mass and 1H n.m.r. spectroscopy).
`t Other spectral parameters of these compounds accord with the proposed structures (i.r., mass, and 1H n.m.r. spectroscopy).
`
`4
`
`

`

`J.C.S. CHEM. CoMM., 1980
`(C-2 + C-6), 27 (C-5), 26·7 [t, 1J(18C-2H) 20Hz, C-3], and
`25 (C-4).t This deuterium-substituted chiral ketone thus
`has the same absolute configuration as that reported by
`Djerassi et al., 4 but is of much higher optical purity (lit., 4
`[8Jmax 47°). The unresolvable mixture of alcohols (4)
`[probably arising from the reduction of (3b) with B.
`sulfurescens] comprises a 50:50 mixture of cis- and trans(cid:173)
`isomers (2H n.m.r. analysis).
`Microbiological reduction of the cyclic IX,B-unsaturated
`ketones (2a) and (2b) with B. sulfurescens thus yields the
`optically active deuterium substituted ketones (3a) and (3b)
`with the S absolute configuration. Both yield and stereo(cid:173)
`specificity are very high and only three steps are necessary
`starting from the 1,3-dione. Previous results6 on substituted
`
`319
`
`cyclic ketones iead us to believe that (3a) and (3b) are in
`fact optically pure. Furthermore, after the reduction with
`B. sulfurescens of 2-alkyliX,B-unsaturated cyclic ketones, C-2
`has the R absolute configuration. 6 Hence, we conclude that
`the reduction of or.,B-unsaturated cyclic ketones with B.
`sulfurescens corresponds to a trans-addition of hydrogen to
`the double bond through the si face on C-2 andre face on C-3.
`We thank Miss F. Gueritte (Institut de Chimie des Sub(cid:173)
`stances Naturelles, C.N.R.S., Gif-sur-Yvette) for c.d. curves
`and Dr C. Brevard (Brucker Spectrospin, Wissembourg) for
`2H n.m.r. spectra.
`
`(Received, 21st December 1979; Com. 1332.)
`
`1 C. J. Sih foreword inK. Kieslich, 'Microbial Transformations of Non-steroid Cyclic Compounds,' Thieme, Stuttgart, 1976.
`3 M. Miyano, C. R. Dom, F. B. Colton, and W. J. Marsheck, Chem. Comm., 1971, 425; W. W. Andrews and M. P. Kuntsmann, U.S.P.
`3,557,151, 1968 (Chem. Abs., 1971, 74, 88,192q); H. Newman; P. Shu, and W. W. Andrews, U.S.P. 3,616,237, 1970 (Chem. Abs., 1972,
`76, 97,939t).
`a J. W. Simek, D. L. Mattern, and C. Djerassi, Tetrahedron Letters, 1975, 3671.
`'C. Djerassi, C. L. Van Antwerp, and P. Sundararaman, Tetrahedron Letters, 1978, 535.
`s Shy Fuh Lee, G. Barth, K. Kieslich, and C. Djerassi, ]. Amer. Chem. Soc., 1978, 100, 3965; S. G. Levin and B. Gopalakrishnan,
`Tetrahedron Letters, 1979, 699; P. Sundararaman and C. Djerassi, ibid., 1978, 2457.
`6 A. Kergomard, M. F. Renard, and H. Veschambre, Tetrahedron Letters, 1978, 5197.
`7 W. F. Gannon and H. 0. House, Org. Synth., 1960, 40, 14.
`
`Polymer-bound Alkali Metal Aromatic Radical Anions
`
`By DAVID E. BERGBREITER* and jAMES M. KILLOUGH
`(D_epartment of Chemistry, Texas A&M University, College Station, Texas 77843)
`
`Summary Polystyrene-bound anthracene has been pre(cid:173)
`pared and found to react with sodium-naphthalene to
`give a polymeric radical anion whose chemistry is
`analogous to that of soluble alkali metal aromatic
`radical anions.
`
`polystyrene. Subsequent treatment of the polymer bound
`tertiary alcohol
`·with
`toluene-p-sulphonic acid in hot
`benzene yielded polystyrylanthracene (equation 1). Re(cid:173)
`duction of this polymeric polycyclic aromatic compound
`with a tetrahydrofuran (THF) solution of sodium-naphtha(cid:173)
`lene according to equation (2) yields the polymeric radical
`
`FUNCTIONALIZED organic polymers containing reactive
`pendant groups are proving to be useful in both polymer
`cheinistry and organic synthesis.1
`In this report we
`describe the first synthesis of an alkali metal aromatic
`·radical anion bound to an organic polymer. !n addition,
`examples of reactions of this polymeric organometallic
`reagent with organic and inorganic substrates are detailed.
`
`@-u +etc
`
`/
`
`~
`~ (2)
`
`@
`HO
`
`( 1)
`
`(1)
`
`A functionalized polymeric precursor to a polymeric
`aromatic radical anion is readily prepared by addition of an
`ethereal solution of anthrone to lithiated macroreticular
`
`anion. Formation of this metallated polystyrene radical
`anion is accompanied by rapid decoloration of the THF
`solution of sodium-naphthalene and concomitant develop(cid:173)
`ment of a dark blue-green colour on the polymer. Gas
`chromatographic analysis of the clear supernatant liquid
`over this coloured polymer shows that all the naphthalene
`originally added is present in solution. Aqueous quenching
`
`5
`
`