1, 2, 3-Triphenyl- 1, 2, 3-trithexylcyclotrisilanes : Synthesis and Ring-Opening by Halogens

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Abstract

Reaction of dichlorophenylthexylsilane (thexyl = 1,1,2-trimethylpropyl) with lithium naphthalenide in tetrahydrofuran at −65 °C gave <i>cis</i>,<i>cis</i>- and <i>cis</i>,<i>trans</i>-1,2,3-triphenyl-1,2,3-trithexylcyclotrisilane <b>1</b> (<i>cis</i>,<i>cis</i>-<b>1</b> and <i>cis</i>,<i>trans</i>-<b>1</b>) in yields of 19 and 52%, respectively. The structures of both isomers were determined by X-ray crystallography. The ring-opening reaction of each isomer with bromine leads to the formation of 1,3-dibromo-1,2,3-triphenyl-1,2,3-trithexyltrisilane (<b>2</b>); <i>cis</i>,<i>cis</i>-<b>1</b> gave only (1<i>R</i>,3<i>R</i>)/(1<i>S</i>,3<i>S</i>)-1,3-dibromo-1,2,3-triphenyl-1,2,3-trithexyltrisilane ((1<i>R</i>,3<i>R</i>)/(1<i>S</i>,3<i>S</i>)-<b>2</b>) (87% yield). While <i>cis</i>,<i>trans</i>-<b>1</b> formed (1<i>R</i>,2<i>s</i>,3<i>S</i>)- and (1<i>R</i>,2<i>r</i>,3<i>S</i>)-1,3-dibromo-1,2,3-triphenyl-1,2,3-trithexyltrisilane ((1<i>R</i>,2<i>s</i>,3<i>S</i>)-<b>2</b> and (1<i>R</i>,2<i>r</i>,3<i>S</i>)-<b>2</b>, in 13 and 31% yields) as well as (1<i>R</i>,3<i>R</i>)/(1<i>S</i>/3<i>S</i>)-<b>2</b> (44% yield). The structures of (1<i>R</i>,3<i>R</i>)/(1<i>S</i>,3<i>S</i>)-<b>2</b> and (1<i>R</i>,2<i>r</i>,3<i>S</i>)-<b>2</b> were confirmed by X-ray crystallography. From the stereochemical results observed in the ring-opening reactions, it is concluded that the cleavage of the Si–Si bonds occurs with retention–inversion of the configuration of the silicon atoms. In the chlorination, <i>cis</i>,<i>cis</i>-<b>1</b> gave (1<i>R</i>,3<i>R</i>)/(1<i>S</i>,3<i>S</i>)-1,3-dichloro-1,2,3-triphenyl-1,2,3-trithexyltrisilane ((1<i>R</i>,3<i>R</i>)/(1<i>S</i>,3<i>S</i>)-<b>3</b>, 40% yield) and (1<i>R</i>,2<i>r</i>,3<i>S</i>)-1,3-dichloro-1,2,3-triphenyl-1,2,3-trithexyltrisilane ((1<i>R</i>,2<i>r</i>,3<i>S</i>)-<b>3</b>, 30% yield); <i>cis</i>,<i>trans</i>-<b>1</b> gave (1<i>R</i>,3<i>R</i>)/(1<i>S</i>,3<i>S</i>)-<b>3</b> (33% yield), (1<i>R</i>,2<i>r</i>,3<i>S</i>)-<b>3</b> (14% yield), and (1<i>R</i>,2<i>s</i>,3<i>S</i>)-1,3-dichloro-1,2,3-triphenyl-1,2,3-trithexyltrisilane in 40% yield. The structure of (1<i>R</i>,2<i>r</i>,3<i>S</i>)-<b>3</b> was confirmed by X-ray crystallography. The result indicates that stereoselectivity was lower in the ring-opening by chlorine than in that by bromine.

Journal

  • Bulletin of the Chemical Society of Japan

    Bulletin of the Chemical Society of Japan 71(10), 2449-2458, 1998-10-15

    The Chemical Society of Japan

References:  33

  • <no title>

    MATSUMOTO H.

    Angew. Chem. Int. Ed. Engl. 31, 1354, 1992

    Cited by (7)

  • <no title>

    UNNO M.

    Organometallics 13, 4633, 1994

    Cited by (7)

  • <no title>

    UNNO M.

    Organometallics 14, 4004, 1995

    Cited by (7)

  • <no title>

    UNNO M.

    J. Organomet. Chem. 521, 409, 1996

    Cited by (4)

  • <no title>

    UNNO M.

    Organometallics 15, 2413, 1996

    Cited by (6)

  • <no title>

    UNNO M.

    Organometallics 16, 4428, 1997

    Cited by (4)

  • <no title>

    MATSUMOTO H.

    J Chem. Soc., Chem. Commun. 1985, 1366

    Cited by (1)

  • <no title>

    MATSUMOTO H.

    Chem. Lett. 1985, 1005

    Cited by (2)

  • <no title>

    MATSUMOTO H.

    J. Chem. Soc. Chem. Commun. 1986, 1768

    Cited by (4)

  • <no title>

    KYUSHIN S.

    Organometallics 13, 795, 1994

    Cited by (3)

  • <no title>

    UNNO M.

    Bull. Chem. Soc. Jpn. 70, 2749, 1997

    Cited by (3)

  • <no title>

    MATSUMOTO H.

    J. Chem. Soc., Chem. Commun. 1987, 1316

    Cited by (12)

  • <no title>

    MATSUMOTO H.

    Chem. Lett. 1988, 629

    Cited by (10)

  • <no title>

    KANEMITSU Y.

    Solid State Commun. 86, 545, 1993

    Cited by (5)

  • <no title>

    KYUSHIN S.

    J. Phys. Soc. Jpn., Suippl. B 63, 46, 1994

    Cited by (1)

  • <no title>

    KYUSHIN S.

    Chem. Lett. 1994, 221

    Cited by (9)

  • <no title>

    KYUSHIN S.

    Chem. Lett. 1995, 815

    Cited by (7)

  • <no title>

    WEIDENBRUCH M.

    Tin and Lead Compounds 9, 19, 1986

    Cited by (1)

  • <no title>

    WEIDENBRUCH M.

    Angew. Chem., Int Ed Engl. 25, 1129, 1986

    Cited by (1)

  • <no title>

    WATANABE H.

    Bull. Chem. Soc. Jpn 60, 769, 1987

    Cited by (1)

  • <no title>

    WEIDENBRUCH M.

    Angew. Chem., Int Ed Engl. 34, 1085, 1995

    Cited by (1)

  • <no title>

    WEIDENBRUCH M.

    Chem. Ber. 129, 401, 1996

    Cited by (1)

  • <no title>

    TAKEDA A.

    Nippon Kagaku Zassi 78, 999, 1957

    Cited by (1)

  • <no title>

    WEIDENBRUCH M.

    Chem. Rev 95, 1479, 1995

    Cited by (2)

  • <no title>

    BELLUCCI G.

    J. Am. Cham Soc. 117, 12001, 1995

    Cited by (1)

  • <no title>

    BIANCHINI R.

    Angew. Chem., Int. Ed. Engl 36, 1284, 1997

    Cited by (1)

  • <no title>

    LAMBERT J. B.

    Angew. Chem., Int. Ed. Engl. 36, 400, 1997

    Cited by (9)

  • <no title>

    TOBITA H.

    Chem. Lett. 1987, 224

    Cited by (2)

  • <no title>

    KAWANO Y.

    J.Organomet., Chem. 428, 125, 1992

    Cited by (10)

  • <no title>

    BORLA M. C.

    J. Appl Cryst 22, 389, 1989

    Cited by (1)

  • <no title>

    teXsan : Crystal Structure Analysis Package, 1992

    Cited by (53)

  • <no title>

    HAI-FU F.

    Structure Analysis Programs with Intelligent Control, 1991

    Cited by (4)

  • <no title>

    KYUSHIN S.

    J. Organomet. Chem 499, 235, 1995

    DOI  Cited by (2)

Codes

  • NII Article ID (NAID)
    10008937713
  • NII NACSIS-CAT ID (NCID)
    AA00580132
  • Text Lang
    ENG
  • Article Type
    ART
  • ISSN
    00092673
  • NDL Article ID
    4583852
  • NDL Source Classification
    ZP1(科学技術--化学・化学工業)
  • NDL Call No.
    Z53-B35
  • Data Source
    CJP  NDL  J-STAGE 
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