B(C<sub>6</sub>F<sub>5</sub>)<sub>3</sub>-Catalyzed Hydrosilylation of Vinylcyclopropanes
作者:Peng-Wei Long、Tao He、Martin Oestreich
DOI:10.1021/acs.orglett.0c02751
日期:2020.9.18
reported. For the majority of VCPs, little or no ring opening of the cyclopropyl unit is observed. Conversely, for VCPs with bulky R groups, such as ortho-substituted aryl rings or branched alkyl residues, ring opening is the exclusive reaction pathway. This finding is explained by the thwarted hydride delivery to a sterically shielded, β-silicon-stabilized cyclopropylcarbinyl cation intermediate.
据报道,强硼路易斯酸B(C 6 F 5)3催化乙烯基环丙烷(VCP)的硅氢化。对于大多数VCP,观察到很少或没有环丙基单元的开环。相反,对于具有庞大R基团的VCP,例如邻位取代的芳基环或支链烷基残基,开环是唯一的反应途径。这一发现可以通过阻止氢化物向空间屏蔽的,β-硅稳定的环丙基羰基阳离子中间物的传递来解释。
Derivatives of indole-2-carboxamides and of azaindole-2-carboxamides substituted with a silanyl group, preparation thereof and therapeutic use thereof
申请人:Dubois Laurent
公开号:US08399491B2
公开(公告)日:2013-03-19
This disclosure relates to compounds of formula (I):
wherein G1, G2, G3, G4, n, Y, Z, Z1, Z2, Z3, and Z4 are as defined in the disclosure, or a salt thereof, or a hydrate or solvate thereof, and to processes for the preparation of these compounds and the therapeutic use thereof.
DERIVATIVES OF INDOLE-2-CARBOXAMIDES AND OF AZAINDOLE-2-CARBOXAMIDES SUBSTITUTED WITH A SILANYL GROUP, PREPARATION THEREOF AND THERAPEUTIC USE THEREOF
申请人:DUBOIS Laurent
公开号:US20110009365A1
公开(公告)日:2011-01-13
This disclosure relates to compounds of formula (I):
wherein G
1
, G
2
, G
3
, G
4
, n, Y, Z, Z
1
, Z
2
, Z
3
, and Z
4
are as defined in the disclosure, or a salt thereof, or a hydrate or solvate thereof, and to processes for the preparation of these compounds and the therapeutic use thereof.
modification in syntheticchemistry but it remains a formidable challenge to perform on unstrained skeletons. Herein, we describe a radical addition-enabled C–C σ-bond cleavage/reconstruction reaction of unstrained allyl ketones to access various functional indanones bearing a benzylic quaternary center. The synthetic utility of this method has been showcased by the first total synthesis of carexane L, an indanone-based
C-C σ 键断裂和重建是合成化学中结构修饰的重要工具,但在无应变骨架上进行仍然是一个巨大的挑战。在此,我们描述了无张力烯丙基酮的自由基加成C-C σ-键裂解/重建反应,以获得带有苄基四元中心的各种功能性茚满酮。该方法的合成实用性已通过茚满酮天然产物 Carexane L 的首次全合成得到展示。