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Unified Synthesis of Right Halves of Halichondrins A–C
The Journal of Organic Chemistry ( IF 3.3 ) Pub Date : 2017-08-16 00:00:00 , DOI: 10.1021/acs.joc.7b01283 Kenzo Yahata 1 , Ning Ye 1 , Kentaro Iso 1 , Santhosh Reddy Naini 1 , Shuji Yamashita 1 , Yanran Ai 1 , Yoshito Kishi 1
The Journal of Organic Chemistry ( IF 3.3 ) Pub Date : 2017-08-16 00:00:00 , DOI: 10.1021/acs.joc.7b01283 Kenzo Yahata 1 , Ning Ye 1 , Kentaro Iso 1 , Santhosh Reddy Naini 1 , Shuji Yamashita 1 , Yanran Ai 1 , Yoshito Kishi 1
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The right halves of halichondrins A–C were synthesized by coupling the common C20–C37 building block 9 with the C1–C19 building blocks 10a–c, respectively. Catalytic, asymmetric Ni/Cr-mediated coupling was used for three C–C bond formations. For all cases, the stereochemistry was controlled with the Cr catalyst prepared from the chiral sulfonamide identified via the toolbox approach. For (3 + 4)-, (6 + 7)-, and (9 + 10)-couplings, the stereoselectivity of 28:1, >40:1, and ∼20:1 was achieved by the Cr catalysts prepared from (S)-H, (S)-I, and (R)-L, respectively. Unlike the first and second couplings, the third coupling used the structurally complex nucleophile. It was demonstrated that the coupling efficiency was excellent even with the electrophile/nucleophile molar ratio = 1.0/1.1. In addition, the third coupling was achieved with the substrate bearing a free hydroxyl group. The products obtained in the Ni/Cr-mediated couplings were converted to the right halves of halichondrins A–C in excellent overall yields. The right halves of halichondrins A–C (1a–c) were synthesized in 28, 24, and 24 steps from commercial d-galactal in 13.4%, 21.1%, and 16.7% overall yield, respectively.
中文翻译：
葫芦素A–C右半部分的统一合成
通过分别将共同的C20-C37结构单元9与C1-C19结构单元10a - c耦合，合成了右半部分的软骨素A-C 。催化的，不对称的Ni / Cr介导的偶联被用于三个C–C键的形成。对于所有情况，均采用通过工具箱方法鉴定的由手性磺酰胺制备的Cr催化剂控制立体化学。对于（3 + 4）-，（6 + 7）-和（9 + 10）偶联，通过（S）-H，（S）-I和（R）-大号，分别。与第一和第二偶联不同，第三偶联使用结构复杂的亲核试剂。已经证明，即使亲电试剂/亲核试剂的摩尔比＝ 1.0 / 1.1，偶联效率也优异。另外，第三偶联是通过带有游离羟基的底物实现的。在Ni / Cr介导的偶联中获得的产物以优异的总收率被转化为halichondrins A-C的右半部分。分别从商业d-半乳糖分28、24和24个步骤合成了右半数的halichondrins A-C（1a – c），总产率分别为13.4％，21.1％和16.7％。
更新日期：2017-08-16
中文翻译：
葫芦素A–C右半部分的统一合成
通过分别将共同的C20-C37结构单元9与C1-C19结构单元10a - c耦合，合成了右半部分的软骨素A-C 。催化的，不对称的Ni / Cr介导的偶联被用于三个C–C键的形成。对于所有情况，均采用通过工具箱方法鉴定的由手性磺酰胺制备的Cr催化剂控制立体化学。对于（3 + 4）-，（6 + 7）-和（9 + 10）偶联，通过（S）-H，（S）-I和（R）-大号，分别。与第一和第二偶联不同，第三偶联使用结构复杂的亲核试剂。已经证明，即使亲电试剂/亲核试剂的摩尔比＝ 1.0 / 1.1，偶联效率也优异。另外，第三偶联是通过带有游离羟基的底物实现的。在Ni / Cr介导的偶联中获得的产物以优异的总收率被转化为halichondrins A-C的右半部分。分别从商业d-半乳糖分28、24和24个步骤合成了右半数的halichondrins A-C（1a – c），总产率分别为13.4％，21.1％和16.7％。
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