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    • 6. 发明授权
    • Preparation of 19-nor vitamin D compounds
    • 19-维生素D化合物的制备
    • US5430196A
    • 1995-07-04
    • US302399
    • 1994-09-08
    • Hector F. DeLucaHeinrich K. SchnoesFariba Aria
    • Hector F. DeLucaHeinrich K. SchnoesFariba Aria
    • C07C29/17C07C35/17C07C35/27C07C401/00C07F7/18C07C43/02C07C35/24
    • C07F7/1856C07C401/00Y02P20/55
    • A synthesis of 1.alpha.-hydroxy-19-nor-vitamin D compounds comprises (a) the construction of a 5,8-diol-6-yne intermediate by joining ring-A and ring-C/D portions of the desired end product via the condensation of an acetylenic derivative containing the C/D-ring portion of the desired end product with a cyclic dihydroxy ketone representing the A-ring of the desired end product; (b) the partial reduction of the 6,7 acetylenic triple bond linkage between the A and C/D ring potions to obtain a 5,8-diol-6-ene intermediate; and (c) the reductive removal of the 5,8-oxygen functions to generate the required 5,7-diene end product from which the desired 7-trans(7E)-isomer is purified directly, or after optional double bond isomerization of the 7-cis(7Z)-isomer employing a novel thiophenol-promoted isomerization step.
    • 1α-羟基-19-去甲维生素D化合物的合成包括(a)通过将期望的最终产物的环A和环-C / D部分连接而构建5,8-二醇-6-中间体 通过含有所需最终产物的C / D环部分的炔属衍生物与代表期望最终产物的A环的环状二羟基酮缩合; (b)部分还原A和C / D环部分之间的6,7炔基三键键,得到5,8-二醇-6-烯中间体; 或(c)还原去除5,8-氧官能团以产生所需的5,7-二烯最终产物,从其中直接纯化所需的7-反式(7E) - 异构体,或在任选的双键异构化 使用新的苯硫酚促进异构化步骤的7-顺式(7Z) - 异构体。
    • 9. 发明授权
    • Preparation of 19-nor vitamin D compounds
    • 19-维生素D化合物的制备
    • US5599958A
    • 1997-02-04
    • US448115
    • 1995-05-23
    • Hector F. DelucaHeinrich K. SchnoesFariba Aria
    • Hector F. DelucaHeinrich K. SchnoesFariba Aria
    • C07C29/17C07C35/17C07C35/27C07C401/00C07F7/18
    • C07F7/1856C07C401/00Y02P20/55
    • A synthesis of 1.alpha.-hydroxy-19-nor-vitamin D compounds comprises (a) the construction of a 5,8-diol-6-yne intermediate by joining ring-A and ring-C/D portions of the desired end product via the condensation of an acetylenic derivative containing the C/D-ring portion of the desired end product with a cyclic dihydroxy ketone representing the A-ring of the desired end product; (b) the partial reduction of the 6,7 acetylenic triple bond linkage between the A and C/D ring portions to obtain a 5,8-diol-6-ene intermediate; and (c) the reductive removal of the 5,8-oxygen functions to generate the required 5,7-diene end product from which the desired 7-trans(7E)-isomer is purified directly, or after optional double bond isomerization of the 7-cis(7Z)-isomer employing a novel thiophenol-promoted isomerization step.
    • 1α-羟基-19-去甲维生素D化合物的合成包括(a)通过将期望的最终产物的环A和环-C / D部分连接而构建5,8-二醇-6-中间体 通过含有所需最终产物的C / D环部分的炔属衍生物与代表期望最终产物的A环的环状二羟基酮缩合; (b)部分还原A和C / D环部分之间的6,7炔基三键键,得到5,8-二醇-6-烯中间体; 或(c)还原去除5,8-氧官能团以产生所需的5,7-二烯最终产物,从其中直接纯化所需的7-反式(7E) - 异构体,或在任选的双键异构化 使用新的苯硫酚促进异构化步骤的7-顺式(7Z) - 异构体。
    • 10. 发明授权
    • Intermediates in the preparation of 19-nor vitamin D compounds
    • 中间体制备19-维生素D化合物
    • US5525745A
    • 1996-06-11
    • US410858
    • 1995-03-27
    • Hector F. DeLucaHeinrich K. SchnoesFariba Aria
    • Hector F. DeLucaHeinrich K. SchnoesFariba Aria
    • C07C29/17C07C35/17C07C35/27C07C401/00C07F7/18
    • C07F7/1856C07C401/00Y02P20/55
    • The invention describes intermediates for use in the synthesis of 1.alpha.-hydroxy-19-nor-vitamin D compounds. The intermediates have the following formula: ##STR1## The disclosed process includes (a) the construction of a 5,8-diol-6-yne intermediate by joining ring-A and ring-C/D portions of the desired end product via the condensation of an acetylenic derivative containing the C/D-ring portion of the desired end product with a cyclic dihydroxy ketone representing the A-ring of the desired end product; (b) the partial reduction of the 6,7 acetylenic triple bond linkage between the A and C/D ring portions to obtain a 5,8-diol-6-ene intermediate; and (c) the reductive removal of the 5,8-oxygen functions to generate the required 5,7-diene end product from which the desired 7-trans(7E)-isomer is purified directly, or after optional double bond isomerization of the 7-cis(7Z)-isomer employing a novel thiophenol-promoted isomerization step.
    • 本发明描述了用于合成1α-羟基-19-去甲维生素D化合物的中间体。 中间体具有以下分子式:所公开的方法包括(a)通过将期望的最终产物的环A和环-C / D部分连接到所述中间体上来构建5,8-二醇-6-中间体 含有所需最终产物的C / D环部分的炔属衍生物与表示所需最终产物的A环的环状二羟基酮缩合; (b)部分还原A和C / D环部分之间的6,7炔基三键键,得到5,8-二醇-6-烯中间体; 或(c)还原去除5,8-氧官能团以产生所需的5,7-二烯最终产物,从其中直接纯化所需的7-反式(7E) - 异构体,或在任选的双键异构化 使用新的苯硫酚促进异构化步骤的7-顺式(7Z) - 异构体。