手性合成英文-2

Elias

J.

Corey－－Autobiography19281944195019561959born

in

Methuen，Massachusettsentered

M.I.T.参与合成青霉素completed

doctoral

workjoined

University

of

Illinoisbecame

Professor

of

Chemistrywork

in

Harvard1957年Elias

J.Corey

提出了他的想法：The

Logic

of

Chemical

Synthesisretrosynthetic

analysis逆合成法The

logic

of

chemical

synthesis简单的原料复杂的分子synthesistransform反合成分析法

retrosynthetic

analysisretrosynthetic

analysisRetrosynthetic

tree树枝－－原料BestChoice?树根－－目标分子位置控制保护基活化基桥连因子To

build

"left-

or

right

handed"

moleculesHerbert

C.

BrownUSAPurdue

University West

Lafayette, IN,

USA1912

-Georg

WittigFederal

Republic of

GermanyUniversity

of Heidelberg Heidelberg, Germany1897

-

1987The

Nobel

Prize

in

Chemistry

1979Laureates:

Herbert

C.

BrownGeorg

Wittig"

for

their

development

of

theuse

of

boron-

and

phosphorus-containing

compounds,respectively,

into

importantreagents

in

organic

synthesis"Boron

compoundsHerbert

C

Brownsodium

boro-hydride(硼氢化钠)--

the

reagent

of

choice

for

reduction of

carbonyl

compoundsOrganoboranes(B2H6)(the

most

versatile

reagents

ever

created

inorganic

chemistry)can

be

used

for

reductions, rearrangements

and

additions

and have

opened

up

a

range

of

new possibilities

for

linking

carbon atoms

to

each

other.还原重排加成Wittig

reactionorganic

phosphorus

compound

with

aformal

double

bond(含双键的有机磷化合物，双键在P和C之间)between

phosphorusand

carbon

react

with

a

carbonylcompound(羰基化合物).The

oxygen

of

the

carbonyl

compound is

exchanged

for

carbon,the

product being

an

olefin(烯烃)。A

carbonylcompound(羰基化合物)这是我们熟悉的Wittig试剂，用于双键化合物的制备organic

phosphorus

compoundwith

a

formal

double

bondbetween

phosphorus

and

carbonolefin(烯烃)Fig

1Fig.1.Formation

of

a

diradical被削弱的C-C键demetalization有机金属锂化合物diradicalFormation

and

characterization

of

compound

9zinc

dust

distillation.芳基质子作为取代基的不稳定性惊人发现：umpolung

规则或极性逆转规则F的特异性Reversal

of

polarity

(umpolung)极性逆转Mechanism

of

formation

of

o-lithiobiphenylProof

of

the

intermediate

occurrence

of

dehydrobenzene

in

the

reaction

of

14

C-labeled

chlorobenzene

with

potassium

amide

in

liquidammoniaFig.

8.

Proof

of

the

existence

of

dehydrobenzenethrough

the

formation

of

10苯炔中间体存在的证实：在反应过程中加入二烯体呋喃，分离出产物10a

Diels-Alder

addition：经证实，苯炔中间体存在的时间为：20

milliseconds.Thermal

decomposition

reactions

used

to

determinethe

lifetime

of

dehydrobenzene

in

the

gas

phase四烷基铵盐上的碳上的氢是否也有不稳定性？通过：氯化四甲基铵甲基锂五甲基氮失败！Formation

of

NylidesylideFormation

of

P-ylidesN-ylide(氮叶立德)The

semipolar

nature

of

the

N-C

bondIts

ability

to

add

to

benzophenone（二 苯甲酮）P-ylide（磷叶立德）triphenylphosphineoxidetriphenylphosphinemethylene

1，1-diphenylethyleneFig.

13.

Steps

in

the

reaction

oftriphenylphosphinemethylene

withbenzophenone四元环过度态应用：vitamin

A的合成硼也可以作为

tetracoordinate

central

atom参考文献E.J.

Corey,

X.-M.

Cheng:

The

Logic

of

ChemicalSynthesis,

Wiley

–

Interscience,

1989.E.J.

Corey,

A.K.

Long,

S.D.

Rubenstein:Computer-Assisted

Analysis

in

OrganicSynthesis,

Science,

Vol

228,

1985,

pp

408-418.The

Royal

Swedish

Academy

of

Sciences,Information

about

the

Nobel

Prize

in

Chemistry1990

(press

release).Further

readingG.

Wittig

and

M.

Rieber,

ibid.

562,

187

(1949).G.

Wittig

and

K

Clauss,

ibid.

577,

26

(1952);

ibid.578,136

(1952).G.

Wittig

and

K.

Torssell,

Acta

Chem.

Stand.

7,1293

(1953).H.

Pommer,

Angew.

Chem.