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有机合成反应. 唐 勇 金属有机化学国家重点实验室. 烯烃的反应 - 基本反应. § 1-5 Olefin Hydrogenation. Relevant Review articles: Angew. Chem. Int. Edit. 26, 190-203 (1987). Historically, primary stereochemical control designed around analysis of steric environment in vicinity of C=C. 烯烃的反应 - 基本反应.

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slide1

有机合成反应

唐 勇

金属有机化学国家重点实验室

Shanghai, China

slide2

烯烃的反应-基本反应

§ 1-5 Olefin Hydrogenation

Relevant Review articles: Angew. Chem. Int. Edit. 26, 190-203 (1987).

Historically, primary stereochemical control designed around analysis of steric environment in vicinity of C=C.

Shanghai, China

slide3

烯烃的反应-基本反应

§ 1-5-1The influence of polar effects-Pd

Thompson, J.Org. Chem. 36, 2577 (1971)

Shanghai, China

slide4

烯烃的反应-基本反应

Polar functional groups may play a role in controlling the diastereoselectivity of the hydrogenation process;

however, the control elements were not well-defined.

J. E. McMurry et al. Tetrahedron Lett.. 3731 (1970)

Shanghai, China

slide6

烯烃的反应-基本反应

The first rational attempt to identify those FGs which will direct the reaction

H. Thopson JACS 1973,95,838.

Shanghai, China

slide7

烯烃的反应-基本反应

§ 1-5-2The influence of polar effects-Cationic Catalysts

Shanghai, China

slide8

烯烃的反应-基本反应

The first rational attempt to associate catalyst with substrate

H. Thopson JACS 1974,96,6232.

Shanghai, China

slide9

烯烃的反应-基本反应

Mechanism of Hydrogenation Cationic Rhodium-(I) Catalysts.

Shanghai, China

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烯烃的反应-基本反应

Mechanism of Hydrogenation Cationic Rhodium-(I) Catalysts.

That H atom lying parallel to the pi-system (HA) should migrate preferentiallyif the dihydride is an intermediate.

Shanghai, China

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烯烃的反应-基本反应

Polar functional groups other than OH may also direct the process

Shanghai, China

slide24

§ 1-6 Olefin Bromination-1

§ 1-6-1 Introduction

Shanghai, China

slide30

Furst-Plattner Rule:

A rigid cyclohexene oxide system: those stereoelectronic effects that operate in ring cleavage also influence ring formation.

Shanghai, China

slide45

Problems of the day:

Shanghai, China

slide52

Hydrohalogenation Reactions of Allenes

  • Allenes:
    • multi-reaction site
    • chirality

Shanghai, China

slide59

JACS, 2003, 12990.

Shanghai, China

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烯烃的反应-基本反应

§ 1-9 Conjugate addition

Michael, J. Prakt. Chem. 1887, 35, 349.

Michael, Am. Chem. J. 1887, 9, 115.

Shanghai, China

slide63

§ 1-9-1 Introduction

Case I

Case II

Shanghai, China

slide64

Addition to a,b-unsaturated compounds:

  • Organoalkali metal reagents from unstabilized carbanion: 1,2-
  • Enolate and other stabilized anion: 1,4-
  • Grignard reagents: 1,2-(aldehyde), 1,4-(Steric ones),
  • 1,2-& 1,4- mixtures (most cases)
  • Organocopper reagents: 1,4-
  • Lithium diorganocopper reagents: 1,4-
  • Cu(I)-Grignard reagents: 1,4-
  • Other nucleophiles:

Shanghai, China

slide70

JACS, 2003, 125,12094.

Shanghai, China