手性合成英文-2

Elias

J.

Corey－－Autobiography19281944195019561959born

in

Methuen，Massachusettsentered

M.I.T.參與合成青霉素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簡單的原料復(fù)雜的分子synthesistransform反合成分析法

retrosynthetic

analysisretrosynthetic

analysisRetrosynthetic

tree樹枝－－原料BestChoice?樹根－－目標(biāo)分子位置控制保護基活化基橋連因子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(硼氫化鈉)--

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.還原重排加成Wittig

reactionorganic

phosphorus

compound

with

aformal

double

bond(含雙鍵的有機磷化合物，雙鍵在P和C之間)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(烯烴)。A

carbonylcompound(羰基化合物)這是我們熟悉的Wittig試劑，用于雙鍵化合物的制備organic

phosphorus

compoundwith

a

formal

double

bondbetween

phosphorus

and

carbonolefin(烯烴)Fig

1Fig.1.Formation

of

a

diradical被削弱的C-C鍵demetalization有機金屬鋰化合物diradicalFormation

and

characterization

of

compound

9zinc

dust

distillation.芳基質(zhì)子作為取代基的不穩(wěn)定性驚人發(fā)現(xiàn)：umpolung

規(guī)則或極性逆轉(zhuǎn)規(guī)則F的特異性Reversal

of

polarity

(umpolung)極性逆轉(zhuǎn)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苯炔中間體存在的證實：在反應(yīng)過程中加入二烯體呋喃，分離出產(chǎn)物10a

Diels-Alder

addition：經(jīng)證實，苯炔中間體存在的時間為：20

milliseconds.Thermal

decomposition

reactions

used

to

determinethe

lifetime

of

dehydrobenzene

in

the

gas

phase四烷基銨鹽上的碳上的氫是否也有不穩(wěn)定性？通過：氯化四甲基銨甲基鋰五甲基氮失敗！Formation

of

NylidesylideFormation

of

P-ylidesN-ylide(氮葉立德)The

semipolar

nature

of

the

N-C

bondIts

ability

to

add

to

benzophenone（二 苯甲酮）P-ylide（磷葉立德）triphenylphosphineoxidetriphenylphosphinemethylene

1，1-diphenylethyleneFig.

13.

Steps

in

the

reaction

oftriphenylphosphinemethylene

withbenzophenone四元環(huán)過度態(tài)應(yīng)用：vitamin

A的合成硼也可以作為

tetracoordinate

central

atom參考文獻(xiàn)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.