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NT)LRU ?VV D:AD ] F egKMLNVX H ] H K^] H L D:F K!M D ]NTÛ¤ H ] H LR HZY TGLVX H ] H KMRVTD L

FIH RXKMLTYF:YDMA K ? H L HZY KMLNK ?_SL HZY hTBVX HZ?BH RV8] DM\ XT?BHZY O

LVX HZY8H K^]VTGR ?BHZY eVX H KM5VX D ] Y R D LSL H VX H TB]NTY RU YY TD LV D VX H?N%O%PRQ$K6S0I3G

T

O%QUVP3GWSYX

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KMLNK

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AD ]VX H4> N·'¸ FIH RXKMLTYF TGL Y V H KMN DMA¦> N·'jTGL HZ?BH RV8] DM\ XT?TGRKMNNTBVTD L Y V D K ?_SL HZY e

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]

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Y

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L/V iH

Vbh HUH

L

VX HZY8H Vbh D KM5VX D ] Y O;WXTY hT?G?giH NTY RU YY8H N A5]VX H ]TGLVX HADE?G?BD hTGL5d5O

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i]_qsl`bn

WX HHZ?BH RV8] DM\ XT?TGR@KMNNTBVTD L] H KMRVTD LTY+D L H4DMA VX H.FIDEY Vd H L H ]K ? KMLN Y8HUA ?

] H KMRVTD L DMA K ? H L HZY KMLNK ?_SL HZY+AD ] Y _SL/VX H VTGR \ 5] \DEY8HZY O LVXTY RXK \ V H ]ZegTBVTY

AD RU Y8H N D L] H KMRVTD L Y VXK^V \ ] D R HUH NVX5] D 5dEX \DE?K^]TGL/V H ] FIH NTGK^V HZYD ]V8]KML Y TBVTD L

Y VK^V HZY OWX H ] H K Y8D L AD ]VXTY e5TY VX H R D ]] HZ?K^VTD LV D ] HZY ?V Y+A] DEF \ X D V DHZ?BH RV8] D L

Y8\H

RV8]

DEY

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Wh D a H ]_TFI\D ]VKML/V] H KMRVTD L FIH RXKMLTYF:Y TGL HZ?BH RV8] DM\ XT?TGRKMNNTBVTD L] H KMRVTD L Y

K^] H VX H4> N·;jKMLN > N·'¸ FIH RXKMLTYF:Y

¸ e £ OQWX H4Y _ F.iDE?> N·'j Y TBdELTÛ HZY VXK^V

VX H.FIH RXKMLTYF TY K i TFIDE?BH RU ?K^] Y8H R D LN D ]N H ]] H KMRVTD LhTBVX] HZY8\H RVV D VX H

K ? H L Hu K ?_SL H KMLN HZ?BH RV8] DM\ XT?BH O'WXTYFIH RXKMLTYF d DHZY VX5] D 5dEXK:RUK^] iD RUK^VTD L

TGL/V H ] FIH NTGK^V H T?G? Y V8]K^V H NTGLgdE5] H l KMLNgdE5] H jO LVXTY RUK Y8H KMLK ? H L H TY Y8H N

TGLVX H ] H KMRVTD LK Y KML H~ K FI\g?BH O

LVX H VX5] HUHbY V HU\ ] H KMRVTD LeVX H ] H TY K \ ]TD ]NTYY8D RUTGK^VTD L Y V HU\DMA VX H4HZ?BH RV8] DM\ XT?TGR

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WX H4> N·'¸ FIH RXKMLTYF TY KIV H ] FIDE?BH RU ?K^]VXTB]N D ]N H ]] H KMRVTD LhTBVX] HZY8\H RVV D

VX H K ? H L

Hu

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K^d

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L/V

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Y TF ?VKML HUD Y?_hTBVXVX H N D ig?BHD ]V8]T\g?BHiD LN H NRUK^] iD LK^V DEF:Y4v-S6KwUVI3x<K+F K^STGL5d

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WX H ] H K^] H.F KML/_ AKMRV D ] Y N H V H ] F TGLTGL5dhXTGRX FIH RXKMLTYF V DADE?G?BD h4O;WX H

Y V H ] HUD RX HZF TY V8]_KMLN Y igY VTBV H L/V Y+DMA VX H K ? H L HZYu K ?_SL HZY e] H KMRVTD LR D LNTBVTD L Y

V HZFI\H ]K^V5] H KMLN \ ] HZYY 5] H¥ e5] H K^d H L/V Y eKMLNR D LR H L/V8]K^VTD L YDMA ] H K^d H L/V Y K^] H.Y8DEFIH

DMA VX HAKMRV D ] Y O L Y8H RVTD L l Ol OµegVX H.Y V H ] HUD RX HZF TY V8]_ DMA¦HZ?BH RV8] DM\ XT?TGR@KMNNTBVTD LV D

K ?T\ XK^VTGRK ? H L HZY KMLNK ?_SL HZY hT?G?iH NTY RU YY8H NO¦XK^VK iD 5VVX H.Y igY VTBV H L/V

H ¤ H RV YDMA VX H K ? H L HZY KMLNK ?_SL HZY

-A KMLK ? H L H4D ]K ?_SL H RUK^]]_K Y V8] D L5d HZ?BH RV8] D LhTBVXN5]KZhTGL5d Y igY VTBV H L/V

Y

TBVK^V

H

NR

?BDEY8H

V D VX

H N D ig?BHD

]V8]T

\g?BH@iD

LNeSVX

H

RUK^]

iD

RUK^VT

D

LTGL/V H ]

FIH

NTGK^V

H

TGLKML

H a H L/VK ?> N·'j FIH RXKMLTYF TY+H~S\H RV H NVD:iH ] HZ?K^VTBa HZ?_L Y VK ig?BH O L D ]N H ]V D

(7)

E Y E ⁺ ⁺ Y -

E ⁺ ⁺

R ₁

R ₃ R ₄

R ₂ R ₁

R ₃ R ₄ R ₂ E

+

R ₁

R ₃ R ₄ R ₂ E

+ + Y -

R ₁

R ₃ R ₄ R ₂ E

Y

¦TBdE5]

H l ÿ2>

VX5]

HUHY

V

HU\

T

?G?

Y V8]K^VT

D L DMA

VX H>

N·'j FIH

RXKMLT YF

hX H ]

H)

TY VX

H

HZ?BH RV8] DM\ XT?BH KMLNã=T Y VX H LR ?BHUDM\ XT?BH O

E Y ⁺

R ₁

R ₃ R ₄

R ₂ R ₁

R ₃ R ₄

R ₂ E

+ + Y -

R ₁

R ₃ R ₄

R ₂ E

+ + Y -

R ₁

R ₃ R ₄

R ₂ E

Y

¦TBdE5] H j ÿ> Vbh DY V HU\ T?G? Y V8]K^VTD L DMA VX H> N·'j FIH RXKMLTYF hX H ] H9 TY VX H.HZ?BH R

V8] DM\ XT?BH KMLNãoTY VX H LR ?BHUDM\ XT?BH O

(8)

E Y ⁺ R ₁

R ₃ R ₄

R ₂ R ₁

R ₃ R ₄ R ₂

R ₁

R ₃ R ₄ R ₂ Y

E 2

E Y E Y

R ₁

R ₃ R ₄ R ₂

E Y E Y

+ E Y

¦TBdE5] H ¸ ÿ> Vbh DY V HU\ T?G? Y V8]K^VTD L DMA VX H> N·'¸ FIH RXKMLTYF hX H ] H9 TY VX H.HZ?BH R

V8] DM\ XT?BH KMLNãoTY VX H LR ?BHUDM\ XT?BH O

Y VK i T?TB½ H VXTY TGL/V H ] FIH NTGK^V H egTBVTY L H R HZYY K^]_VD:D ]TH L/VK:LR ?BHUDM\ XT?BH V D VX H

RUK^] iD RUK^VTD LK^VVX H.Y K FIH VTFIH K Y VX H4HZ?BH RV8] DM\ XT?BH TY KMNN H NV D VX H K ? H L H4D ]

K ?_SL H O;WXTY TY VX H.> N·'¸ FIH RXKMLTYF KMLNTYH~S\H RV H NV DiH VX H N DEF TGLK^VTGL5d

FIH RXKMLTYF TGLVXTY RUK Y8H OWXTY TY L D VL H R HZYY K^]T?_VX H RUK Y8H TGLK ?G?HZ?BH RV8] DM\ XT?TGR

KMNNTBVTD L] H KMRVTD L Y V D K ? H L HZY KMLNK ?_SL HZY hTBVX Y V8] D L5d HZ?BH RV8] D LhTBVXN5]KZhTGL5d

Y igY

VTBV

H

L/V Y e

iH

RUKM

Y8H

VX

H

TGLVy

H

LR HDMA'F

KML/_

D

VX H ] A

KMRV D ]

Y?

TB

H

VX DEY8H4FIH

L/VT D L H N

K iD a H RUKMLdETBa H K:TBV H NTÛ¤ H ] H L/V] HZY ?VUO'WXTY TY M Y V FIH L/VTD L H NK Y KId H L H ]K ?

H~ K FI\g?BH O Ld H L H ]K ?eVX H K ? H L HZY K^] H4H~S\H RV H NV DADE?G?BD h*VX H.> N·'j FIH RXKMLTYF

hXT

?BH

VX H K ?

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RV

H

NV D:ADE?G?BD

hÚVX H.>

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K ?_SL H TGLKML > N·'j FIH RXKMLTYF TYFID ] H L Y VK ig?BH VXKMLK Y8\

»

X/_ i ]TGNTB½ H N

RUK^]

iD

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DMA

KMLK

? H L H4ADE?G?BD

hTGL5dVX H4Y

K

FIH.FIH

RXKMLT YF

O

cH

RUKM

Y8H.DMA

VXT

Y

e5h

H

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ADE?G?BD h Y VX H.> N·'j FIH RXKMLTYF O > dEKMTGLeVXTY TY L D VL H R HZYY K^]T?_VX H RUK Y8H TA VX H

K ?

_SL HAD

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Y

VKMLR

H

XK

Y

KIa

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N

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D

LN

D

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igY

VTBV

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L/VhXTGRXRUKML

Y VK i T?TB½ H KIaSTGL/_ ? RUK^VTD LTGL/V H ] FIH NTGK^V H TGLKML > N·'j] H KMRVTD LOQWX Y eSVX H RX D TGR H4DMA

FIH RXKMLTYF TY N H LTBV HZ?_L D V DMi aSTD Y O

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XK;ON%O%IX$O}~O%Q$K6Sw9O9D ] XK;ON%O%IXWO%Q@S8Q O > ] H dETDEY8HZ?BH RVTBa H ] H KMRVTD LTY KI] H KMRVTD LhX H ] H

D L H4\ ] D NRVTY+AD ] FIH NTGLdM] H K^V H ]K FID L/VVXKML D VX H ] \DEYY Tig?BH@\ ] D NRV Y O;WX H

V H ] FN%O|9S0I TY\D TGL/VTGL5d9V D h+K^]N Y VX H ] H KMRVTBa H K^V DEFYÏ+DMA VX H.FIDE?BH RU ?BH O >

] H dETDEY8\H RUTÛR@] H KMRVTD LdETBa HZYH~ R ? Y TBa HZ?_ D L ?_ D L H4\ ] D NRVUO;WX H h D ]N YY8HZ?BH RVTBa H

KMLN Y8\H

RUTÛRXKZa

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VX H4Y

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FIH.FIH

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] H KMRVTD L Y e i 5V+TGLVXTY RUK Y8H TBVTYQAD RU Y8H N D LVX H NTÛ¤ H ] H L/V Y V H ] HUD TY8DEFIH ] Y+AD ] FIH NTGL

(9)

HX

Most stable carbocation X -

X

R R

R H

H

Most favourable product

HX

Least stable carbocation X -

Least favourable product 1)

2) R

R R

H

R H

H R

R

+

R

R H

R

R H R

H

+

R

R R

X

H H

¦TBdE5] H£5ÿ Wh D\DEYY Tig?BH ] H KMRVTD L \ K^VX Y TGLhXTGRX \ K^VX

l TY@A KZa D 5] H NN H V D VX H

K^] D aSLTB D a] ?BH O

K:RX HZF TGRUK ? ] H KMRVTD LO -A VX H.bY V H ] HUD TY8DEFIH ]TYAD ] FIH NTGLKIdM] H K^V H ]@K FID L/VVXKML

VX H P TY8DEFIH ]ZeSVXTY TY K Y V H ] HUDEY8HZ?BH RVTBa H ] H KMRVTD LO -A VX H4 TY8DEFIH ]TYAD ] FIH N

H~ R ? Y TBa HZ?_Me5VXTY TY K Y V H ] HUDEY8\H RUTÛR] H KMRVTD L » O

L HZ?BH RV8] DM\ XT?TGR@KMNNTBVTD L Y V D K ? H L HZY KMLNK ?_SL HZY eTBVTY d H L H ]K ?G?_ AD LNVXK^VK

] H dETDEY8HZ?BH RVTBa H ] H KMRVTD LVK^ HZY\g?KMR H OQ D ]@TGL Y VKMLR H e5VX H4F K!MD ] \ ] D NRV AD ] FIH NTGL

KMNNTBVT D L

YDMA

X/_SN5]

D d H

LXK

?

TGN HZY

e

C

eV

D

KMLL Y _

F:FIH

V8]TGRUK

? K ? H L H

egT

Y

VX H4D

L H

hX H ] H TYiD LN H NV D VX H4FIDEY V Y igY VTBV5V H NRUK^] iD LK^V DEF OWXTY RUKML iH

H~S\g?KMTGL H N i _R DEFI\ K^]TGL5dIVX H4Y VK i T?TBVTHZYDMA VX H Vbh D NTÛ¤ H ] H L/VRUK^] iD RUK^VTD L

TGL/V H ]

FIH

NTGK^V HZY

O;WX

H

RUK^]

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D

LhTBVXVX H4\DEY

TBVTBa

H

RXK^]d H.?BD

RUK^V

H

NK^VVX

H

RUK^]

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L

K^V DEF hTBVXVX H.?K^]d HZY V Y igY VTBV H L/V Y V5]L Y+D 5VV DiH VX H.FIDEY V A KZa D 5]K ig?BH O L

KMNNTBVTD LV D VX HHZ?BH RV8] D LN D LK^VTGL5d H ¤ H RVUegVX H ] H K Y8D L AD ]VXTY TY VX Hi TBdMd H ]

\DEYY Ti T?TBVb_ DMA N HZ?BD RUK ?TB½ZTGL5d9VX H\DEY TBVTBa H RXK^]d H TGLVX H RUK^] iD RUK^VTD LOQWXTY ] H KMRVTD L

XK YADE?G?BD h H NVX HP3N9I3!GWSY9I3?NxV}~O hXTGRX Y VK^V HZY VX HADE?G?BD hTGL5d ÿ

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Y

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H£

hX H ] H ] H

KMRVT D L \

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VX H.FIDEY

V

AKZa D 5]K ig?BH4\ ] D NRVUO

LVX H L H~ V AH h Y8H RVTD L Y egNTÛ¤ H ] H L/V+Vb_ \HZYDMAHZ?BH RV8] DM\ XT?TGRKMNNTBVTD L] H KMRVTD L Y hT?G?

iH NTY RU YY8H NO

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>@YFIH L/VTD L H N H K^] ?TH ]Ze5VX H KMNNTBVTD L DMA X/_SN5] D d H LXK ?TGN HZY TY d H L H ]K ?G?_ AD LNVD

ADE?G?BD

hÚVX H4

K^]

D

aSLTB

D

a]

?BH

OP

DEFIHDMA

VX H4FIH

RXKMLT YF:Y

TGL/a DE?

a H

NTGLVXT

Y

Vb_

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A*@>:#/7W3C06E</#&$"#@&8J0/;#CJ&!#&]/#&!3D7!;%& 9&7!

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(10)

R

R R

R

+ HX Fast R

R R

R HX

Complex

R

R R

R HX

+ HX Slow

R

R R

R

X H

+ HX

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K ? H L H R DEFI\g?BH~ KMLNK Y8H R D LNX/_SN5] D d H LXK ?TGN H O

KMNNTBVTD L] H KMRVTD L Y eK^] H VX H.> N·'jIKMLN > N·'¸ FIH RXKMLTYF:Y O -A VX HZY8H.Y8H R D LNKMLN

VXTB]N D ]N H ]] H KMRVTD L Y K^] H TB]] H a H ] Y Tig?BH eh H RUKMLh]TBV H VX H ] HZY8\H RVTBa H ]K^V H

H~S\

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HZYY

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h

YUÿ

20<@:

R m

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l

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m

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AK Y VK:RX HZF TGRUK ? ] H KMRVTD L D RURU5] Y O cH RUKM Y8H.DMA VXTY+\ ] DM\H ]Vb_MeVXTY+\ K^]K FIH V H ]@RUKML

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l OjOjO

WX H ] H K^] H4D VX H ] \DEYY Tig?BHFIH RXKMLTYF:Y TGLhXTGRX A] HUH]KMNTGRUK ? RXKMTGLKMNNTBVTD L

D RURU5] Y TGLR DEFI\H VTBVTD LhTBVXVX H TD LTGRKMNNTBVTD LO'WX HZY8H ] H KMRVTD L Y K^] H4DMAV H L

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KMNNTBVTD L \ ] D NRVUO'WX HZY8H ] H KMRVTD L Y hT?G? L D V iHA 5]VX H ]NTY RU YY8H NTGLVXTY VX HZY TY O

L > N·'¸IKMNNTBVTD L Y V D K ? H L HZY egK:R DEFI\g?BH~ TY+AD ] FIH N iH Vbh HUH LVX H K ? H L H KMLN

X/_SN5] D d H LXK ?TGN H hTBVXVX H.Y8H R D LNX/_SN5] D d H LXK ?TGN HFIDE?BH RU ?BH O;WXTY XK \\H L Y

iH RUKM Y8HDMA VX H4?TBV8V ?BH4?TB HZ?TGX DD N DMA\ ] D NRVTBa H V H ] FIDE?BH RU ?K^]R DE?G?TY TD L Y O'WXTY TY

T

?G?

Y V8]K^V

H

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(11)

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(12)

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(13)

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(15)

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\ ] HZF TH ]+] HZY8H K^]RXV DDE?AD ]VX H4Y VN5_ DMA¦F K^V8V H ]K Y VX HAKMRUT?TBVTHZY K^] D LNVX H h D ] ?N

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Y _SLRX5] D V8] D L]KMNTGK^VTD LTYi K Y8H N D LVX HBbUVI9KI!O}~O%Q$K6NS0QoO6Ë4O%Q$K eTBVTY LK^V5]K ? V D dETBa H

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VX H4bUVI9KI!O}~O%Q$K6NS0Q,O6Ë4O%Q$K ¹

O;X H L ?TBdEX/V Y V8]RK FIH VK ?Y 5] AKMR H e Y8DEFIH4HZ?BH RV8] D L Y

L H K^]VX H.Y 5] AKMR H K igY8D ] iH N H L D 5dEX H L H ]dM_V D:D a H ]R DEFIH VX H K^V8V8]KMRVTD L DMA VX H

\DEY TBVTBa H TD L Y TGLVX H4FIH VK ? KMLN HZY RUK \H TGL/V D VX H4Y 5]] D LNTGL5d Y8\ KMR H O

'~S\H ]TFIH L/V Y RUK^]]TH N D 5V i _VX H ê H ] F KML \ X/_ Y TGRUTY V Y T?X HZ?GFÁC K ?G?h+KMRX Y KMLN

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egL DI\ X D V DHZ?BH RV8] D L Y K^VK ?G?

(16)

l

VX H4\ X D V DHZ?BH RV8]TGR H ¤ H RVUO

h H ] H4HZF

TBV8V

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NL

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LR_

DMA

VX H4?

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F TGLTF F a^K ? H RUK ?G?BH NVX H

¬¥Å¥ÆÕ®Å¯Ë°#Ìb¥Æ2Ìq±ÆS«²MÎ

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dM] H K^V H ]@VXKMLVX H VX5] HZY X DE?N A] H H LR_Me Y8DEFIHHZ?BH RV8] D L Y h H ] H4HZF TBV8V H N A] DEF VX H

FIH

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?

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DMA

VX H.?

TBdEX/V+h+K

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TGLR] H K Y8H NhXT?BH TBV YA] H H LR_h+K Y R D L Y VKML/VUegVX H RU5]] H L/V ?BH a HZ?BH N D ¤K^VK:XTBdEX H ]

a^K ? H hXTGRX Y X D h H NVXK^V FID ] HHZ?BH RV8] D L Y h H ] HHZF TBV8V H N \H ]VTFIH LTBV+hXT?BH VX H

STGL H VTGR H L H ]dETHZYDMA VX H4\ X D V DHZ?BH RV8] D L Y h H ] H VX H.Y K FIH O CD h H a H ]ZeghX H LVX H

A] H H LR_ DMA VX H.FID L D RX5] DEF K^VTGR ?TBdEX/V+h+K Y TGLR] H K Y8H Ne5VX H STGL H VTGR H L H ]dETHZYDMA

VX H4\ X D V DHZ?BH RV8] D L Y TGLR] H K Y8H N \ ] DM\D ]VTD LK ?G?_MO¦WX HZY8HDMigY8H ]a^K^VTD L Y R D ?NL D V iH

H~S\g?KMTGL H N i _R ?K YY TGRUK ?FIH RXKMLTGR Y KMLN HZ?BH RV8] D N5_SLK F TGR Y O

WX HDMigY8H ]a H N \ X H L DEFIH LK] HZY ?V A ] DEF VX H,Í@xWP3GbK6x

T

LK^V5] HDMA ]KMNTGK^VTD LO

Q?BH RV8] DEF K^dEL H VTGR]KMNTGK^VTD LXK YiD VXh+KZa H KMLN \ K^]VTGR ?BH\ ] DM\H ]VTHZY O'WX HH L H ]dM_

TGLKML HZ?BH

RV8]

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OWXTY R D ]] H RVKMLK ?_ Y TY h+K Y N H a HZ?BDM\H N i _ >@?BiH ]V TGL Y V H TGLTGL

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¼_ H K^] YH K^] ?TH ] i _ K ~Q?KMLROQWX HH L H ]dM_ DMA K \ X D V D LTYH K ? V D K

R D L Y VKML/V UQ?KMLR éY R D L Y VKML/V VTFIHZY TBV éYA] H H LR_À´ R4TY VX H.Y8\HUH N DMA'?TBdEX/V

jOºMºM¹½ l k9Ò F,u¥YÏ KMLN

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WXTY+H L H ]dM_V8]KML Y8AH ]TY KMLK ?G?ÛD ] L D VXTGL5d \ ] D R HZYY O;WX HHZ?BH RV8] D Ld H V Y K ?G? VX H

H L H ]dM_ DMA VX H4\ X D V D L D ]L D L H K^VK ?G?O -A VXTY+H L H ]dM_TY dM] H K^V H ]@VXKMLVX H ¯g{

Ì-±«²M¬¥³¯«ÔÓ

eVX HHZ?BH RV8] D L F KZ_ HZY RUK \H4A ] DEF VX H4Y 5] AKMR H OQWX HH~ R HZYYH L H ]dM_TY

R D L Y8H ]a H NTGLVX H4HZ?BH RV8] D LK Y STGL H VTGR H L H ]dM_Me 8µ·¶¸ O;WX H ] HZ?K^VTD L Y XT\iH Vbh HUH L

VX H4H L H ]dM_ DMA VX H\ X D V D LeVX H h D ] ALRVTD Le5KMLNVX H STGL H VTGR H L H ]dM_ DMA VX H

HZ?BH RV8] D LTY+H~S\ ] HZYY8H NTGLVX H4ADE?G?BD hTGL5d H K^VTD L wÕ TY VX H.F K YYDMA VX HHZ?BH RV8] D Le

KMLNÀÖ3×8Ø%Ù:TY VX H a HZ?BD RUTBVb_ DMA VX H4HZ?BH RV8] D L ÿ

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ÊgË³È¦ÅÊ5¬¥³²ÊgËw{gÆS«ÆÕ:Êg«°#ÊgËw{Î«ÆÕ

L \ X D V DHZ?BH RV8] D L Y8\H RV8] DEY R DM\ _Me FIDE?BH RU ?BHZY KMLNK^V DEF:Y K^] H R D ] H4D ]a^K ?BH LR H

TD LTB½ H N F K^STGL5dIVX HZF \DEY TBVTBa HZ?_RXK^]d H NOQ D ]VX H.Y K FIH K^V DEF D ] FIDE?BH RU ?BH e5VX H

R D ] H TD LTB½ZK^VTD L H L H ]dM_TY XTBdEX H ]+VXKMLVX H a^K ?BH LR H TD LTB½ZK^VTD L H L H ]dM_MOQWX H ] H K Y8D L

AD ]VXTY TY VX HFID ] H4Y V8] D L5d ?_ HZ?BH RV8] DEY VK^VTGR4K^V8V8]KMRVTD L iH Vbh HUH LVX H R D ] H4HZ?BH RV8] D L Y

KMLNVX H\DEY TBVTBa HZ?_RXK^]d H NLR ?BH Y O;WX H a^K ?BH LR H4HZ?BH RV8] D L Y K^] H4FID ] H.Y XTHZ?N H N

A] DEF VX H LR ?BH Yi _VX H TGLL H ] HZ?BH RV8] D L Y hXTGRX] HZY ?V Y TGL ?BD h H ]@TD LTB½ZK^VTD L

H L H ]dETHZY O

LRX HZF TY V8]_MeRX HZF TGRUK ? ] H KMRVTBaSTBVb_TY KhTGN H R D LR HU\ VUOQWX H ] H K^] H.F KML/_Vb_ \HZYD ]

R ?K YY8HZY+DMA RX HZF TGRUK ? ] H KMRVTD L Y VXK^VRUKMLVK^ H\g?KMR H TGLLK^V5] HD ]TGLVX H?K iD ]K^V D ]_MO

P DEFIHDMA VX HZY8H R ?K YY8HZYDMA ] H KMRVTD L Y RUKML iH LR ?BHUDM\ XT?TGR Y igY VTBV5VTD L YP ¸ l e

P ¸ j e HZ?BH RV8] DM\ XT?TGR@KMNNTBVTD L Y4> N·;je > N·'¸ e HZ?TF TGLK^VTD L] H KMRVTD L Y9

l e l R i e

j egK^] DEF K^VTGR Y igY VTBV5VTD L Y eSR D LR H ]V H N] H KMRVTD L Y egKMLN A] HUH]KMNTGRUK ? ] H KMRVTD L Y O

>@?G?DMA VX HZY8H ] H KMRVTD L YADE?G?BD h*VX H TB] D hLRXK^]KMRV H ]TY VTGR] H KMRVTD L FIH RXKMLTYF:Y hTBVX

D L H4D ] Y8H a H ]K ? ] H KMRVTD L Y V HU\gY O;W D N H V H ] F TGL H VX H ] H KMRVTBaSTBVb_ DMA K:R DEFI\D LN

ADE?G?BD hTGL5dIK Y8\H RUTÛR@] H KMRVTD L FIH RXKMLTYF e5h H L HUH NV D TGL/a HZY VTBdEK^V H.H KMRX] H KMRVTD L

Y V HU\ TGLK:RX HZF TGRUK ? ] H KMRVTD LO

J+X HZF TGRUK ? ] H KMRVTBaSTBVb_RUKML iH4FIH K Y 5] H N i _VX HHN=P9K;O.DMA K Y8\H RUTÛR] H KMRVTD LOQWX H

AK Y V H ]@KI] H KMRVTD L D RURU5]ZeVX H4FID ] H ] H KMRVTBa H K^] H VX H.FIDE?BH RU ?BHZY4K^V DEF:YÏ KMRVTGL5dTGL

VX H ] H

KMRVT

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K^dELTBVN HDMA

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5]

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VKML/VO

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H L/VXK ?B\ _ 0Ú

¡ KMLNêTiigYA] HUH4H L H ]dM_ 0Ú¥Û. O Ú ¡ TY ] HZ?K^V H NV D,Ú¥Û VX5] D 5dEX

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? ] H

KMRVT D L F

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DMA'Y8H

a H ]K

? ] H

KMRVT D L Y V

HU\gY

OQWX H4Y?BD

h

HZY

V

] H KMRVTD L Y V HU\ TY VX HD L H hXTGRXN H V H ] F TGL HZY VX H ]K^V HDMA VX HD a H ]K ?G? ] H KMRVTD LOQWXTY

Y V HU\ TY RUK ?G?BH NVX HHN=P9K;OÞO@K;ON

T

SwGWSwG2|,XK;O; KMLNhT?G? VX H ] HUAD ] H N H RUTGN H VX H ] H KMRVTBaSTBVb_

DMA

VX H R

DEFI\D

LN

YÏ;ADE?G?BD

hTGL5dK Y8\H

RUTÛR FIH

RXKMLT YF

O'WX

H

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H N H V H ] F

TGLTGL5d Y V

HU\

XK Y VX H XTBdEX HZY VKMRVTBa^K^VTD L H L H ]dM_ Ø TGLKI] H KMRVTD LOQWXTY RUKML iH ]K^VTD LK ?TB½ H N

A] DEF VX H4> ]]X H LTG YH K^VTD L ÿ

Ïß

½ Bàá

â9ã

µ

LVXTY+H K^VTD Le5TY VX H ]K^V H R D L Y VKML/VUe > TY VX H4> ]]X H LTG Y R D L Y VKML/VUe TY VX H

(18)

G

Reactant(s)

Product(s) Transition state (TS ₁ )

Transition state (TS ₂ )

Delta G ₁

Delta G ₂

Delta G

Reaction coordinate Intermediates

¦TBdE5] H lMl ÿQD V H L/VTGK ?qH L H ]dM_NTGK^dM]K F:YAD ]KVbh D^bY V HU\ ] H KMRVTD LO

dEK Y R D L Y VKML/VUeKMLNWÚTY VX H K igY8DE?5V H V HZFI\H ]K^V5] H TGL¡ HZ?aSTGLO'WX H ]K^V H R D L Y VKML/V

N5] DM\gY TA VX H KMRVTBa^K^VTD L H L H ]dM_TGLR] H K Y8HZY O LgdE5] H

lMl

egKI] H KMRVTD LR DD ]NTGLK^V H

DMA KVbh D^bY V HU\ ] H KMRVTD LTYY X D hLK Y KML H~ K FI\g?BH O

>@Y h H RUKML Y8HUH e Ú¥Û

TY+? K^]d H ]VXKML Ú¥Û»0Ú TY+H~S\ ] HZYY8H NK Y [

HZ?VK OWXTY+FIH KML Y

VXK^VVX H g] Y V Y V HU\ TY VX H4D L H hTBVXVX H XTBdEX HZY VKMRVTBa^K^VTD L H L H ]dM_ D ]@XTBdEX HZY V

Ú¥Û=Y TGLR H(Ú¥Û TY NTB] H RV ?_ \ ] DM\D ]VTD LK ? V D Ø egKMLNhT?G? VX H ] HUAD ] HiH VX H ]K^V H

N H V H ] F TGLTGL5d Y V HU\ TGLVX H ] H KMRVTD LO

WX H ]K^V H N H V H ] F TGLTGL5d Y V HU\ TY Y K ?G?_:VX H.Y V HU\ hX H ] H RUK^] iD RUK^VTD L Y K^] H4AD ] FIH NO

Q?BH

RV8]

DM\

XT

?

TGR@KMNNTBVT

D

L]

H

KMRVT D L Y TY

KML H~

K

FI\g?BHDMA

K:R

?K YYDMA

] H KMRVT

D L Y

TGLhXTGRX

VX H ]K^V H N H V H ] F TGLTGL5d Y V HU\ TY VX H RUK^] iD RUK^VTD L AD ] F K^VTD LO > VVXTY+\D TGL/VUe5h H RUKML

Y8HUH K Y TF T?K^]TBVb_ iH Vbh HUH L] H KMRVTBaSTBVb_TGL HZ?BH RV8] DM\ XT?TGRKMNNTBVTD L] H KMRVTD L Y KMLN

\ X D V DHZ?BH RV8] D L Y8\H RV8] DEY R DM\ _MO L \ X D V DHZ?BH RV8] D L Y8\H RV8] DEY R DM\ _Megh H L HUH NK:R H ]VKMTGL

K FID L/V H L H ]dM_V D TD LTB½ H K FIDE?BH RU ?BHD ]KMLK^V DEF V D d H VK \ ] D NRV+hTBVXK

\DEY TBVTBa H RXK^]d H OWX H4Y VK^] Y TBdEL ;ä^+i _VX H TD LTB½ H N H VX H L H4FIDE?BH RU ?BH TGLgdE5] H l j

N H L D V HZY VX H TD LTB½ H NRUK^] iD LK^V DEF O cH RUKM Y8H.DMA VX H4HZ?BH RV8] D L H dEK^VTBaSTBVb_ DMA VX H

TD LTB½ H NRUK^] iD LK^V DEF egTBV \ ?G?GY VX Hå)HZ?BH RV8] D L Y V D h+K^]N Y TBV Y8HZ?BA KMLNR] H K^V HZY KML

HZ?BH RV8] D L \ KMTB]hXTGRXT Y?BD RUK ?TB½ H NK^VVX H4Y K FIH RUK^] iD LK^V DEF OQWXTY+HZ?BH RV8] D L

V8]KML Y8AH ] F K^ H VX H4D VX H ]RUK^] iD LK^V DEFÑ\DEY TBVTBa HZ?_RXK^]d H NOTB H hTY8H TGL

HZ?BH RV8] DM\ XT?TGR \ ] D V D LKMNNTBVTD L Y eh H L HUH NK:R H ]VKMTGLKMRVTBa^K^VTD L H L H ]dM_TGL D ]N H ]V D

d H V@KIRUK^] iD RUK^VTD LTGL/V H ] FIH NTGK^V H hTBVXK \DEY TBVTBa H RXK^]d H O L iD VXRUK Y8HZY eVX H ] H TY

K AD ] F K^VTD L DMA¦Y8\H RUTHZY hTBVX \DEY TBVTBa H RXK^]d HZY eKMLNVX H V D VK ? L F.iH ] DMA

L D L

iD

LNTGL5dKMLN iD

LNTGL5d HZ?BH

RV8]

D L Y TY

VX H4Y

K

FIH

O LgdE5]

H l je

H

VX H L

H

J

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Y8H NK Y KML H~ K FI\g?BH O

(19)

H

H H

H

+ H ⁺ Slow

H H

H

+

H

H H

H

+

H

H H

H

*

+ + e ^-

hv

..

¦TBdE5] H l j ÿ K^V H N H V H ] F TGLTGL5d \ ] D V D LK^VTD LKMLNR D ] H TD LTB½ZK^VTD L DMA¦H VX H L H O

a H LVX D 5dEX H L H ]dETHZY TGL/a DE?a H NTGL]K^V H N H V H ] F TGLTGL5d \ ] D V D LK^VTD L Y KMLNR D ] H

TD LTB½ZK^VTD L Y K^] H L D VR DEFI\ K^]K ig?BH eVX HHK6N%OGJÞ TGLK Y8H ]THZYDMA¦FIDE?BH RU ?BHZY K^] H

R DEFI\ K^]K ig?BH O LVXTY VX HZY TY e5VXTYY8H ]THZY hT?G? R D L Y TY V DMA K ? H L HZY KMLNK ?_SL HZY O

>@Y hT?G?iH4Y8HUH LeVX H R D ] H TD LTB½ZK^VTD L H L H ]dETHZY K^] H Y8H NTGL Y V H KMN DMA VX H a^K ?BH LR H

H L H ]dETHZY OQWX H ] H K Y8D L AD ]VXTY TY VX H R DEFI\g?BH~ TBVb_ DMA VX H a^K ?BH LR H4Y8\H RV8]KSO LK

X/_SN5] D RUK^] iD LeSVX H ] H K^] H4FIDE?BH RU ?K^] D ] i TBVK ?GY hTBVXNTÛ¤ H ] H L/V H L H ]dETHZY O;WX HZY8H hT?G?

K ?G? K \\H K^]TGLVX H.Y8\H RV8] F KMLNdETBa H.F KML/_ \H K^ Y hXTGRXK^] H ] HZ?K^VTBa HZ?_NT)LRU ?V

V D KMLK ?_½ H O VTYFID ] H K \\ ] DM\ ]TGK^V H V D R D ] H TD LTB½ H VX H4FIDE?BH RU ?BHZY O LVXTY RUK Y8H eTBV

TY ] HZFID a H N HZ?BH RV8] D L YA] DEF VX H l

YD ] i TBVK ? TGLVX H RUK^] iD LK^V DEF:Y OWX H ] HZY ?V DMA

VXTY TY K Y8\H RV8] F hTBVX AH h H ]h HZ?G? N H L H N \H K^ Y.VX H L F.iH ] DMA\H K^ Y TY

H TBa^K ?BH L/VhTBVXVX H L F.iH ] DMA RX HZF TGRUK ?G?_TGL H TBa^K ?BH L/VRUK^] iD LK^V DEF:YÏ OWX HZY8H

Y8\H RV8] F:Y K^] H.FID ] HH K Y _V D KMLK ?_½ H egKMLNVX H ] HUAD ] H VX H.FIDE?BH RU ?BHZY K^] H R D ] H

TD LTB½ H NTGL Y V H KMN DMA a^K ?BH LR H TD LTB½ H NO LVXTY RUK Y8H egh H K^] H L D VTGL/V H ] HZY V H NTGLVX H

H L H ]dM_ ?BH a HZ?GYDMA VX H NTÛ¤ H ] H L/Va^K ?BH LR HD ] i TBVK ?GY O'XK^Vh H h+KML/VUeTY V D Y8H VX H

H L H ]dETHZYA] DEF VX H4H~S\H ]TFIH L/VK ?Y8\H RV8] F TGL D ]N H ]V D dEKMTGLTGL Y TBdEX/VTGLRX HZF TGRUK ?

] H

KMRVTBaSTBVb_MO

LKMNNTBVT

D

Le5NTÛ¤

H ] H

L/V

\ ] D R HZYY8HZY

VK^STGL5d

\g?

KMR

H

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RU

?BHZY

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(20)

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(21)

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Core photoelectron spectroscopy and chemical reactivity of a series of aliphatic alkenes and alkynes

E Y E + + Y -

E + +

R 1

R 3 R 4

R 2 R 1

R 3 R 4 R 2 E

+

R 1

R 3 R 4 R 2 E

+ + Y -

R 1

R 3 R 4 R 2 E

Y

E Y +

R 1

R 3 R 4

R 2 R 1

R 3 R 4

R 2 E

+ + Y -

R 1

R 3 R 4

R 2 E

+ + Y -

R 1

R 3 R 4

R 2 E

Y

E Y + R 1

R 3 R 4

R 2 R 1

R 3 R 4 R 2

R 1

R 3 R 4 R 2 Y

E 2

E Y E Y

R 1

R 3 R 4 R 2

E Y E Y

+ E Y

HX

Most stable carbocation X -

X

R R

R H

H

Most favourable product

HX

Least stable carbocation X -

Least favourable product 1)

2) R

R R

H

R H

H R

R

+

R

R H

R

R

R H R

H

+

R

R R

X

H H

R

R R

R

+ HX Fast R

R R

R HX

Complex

R

R R

R HX

+ HX Slow

E Y E ⁺ ⁺ Y -

E ⁺ ⁺

R ₁

R ₃ R ₄

R ₂ R ₁

R ₃ R ₄ R ₂ E

R ₁

R ₃ R ₄ R ₂ E

R ₁

R ₃ R ₄ R ₂ E

E Y ⁺

R ₁

R ₃ R ₄

R ₂ R ₁

R ₃ R ₄

R ₂ E

R ₁

R ₃ R ₄

R ₂ E

R ₁

R ₃ R ₄

R ₂ E

E Y ⁺ R ₁

R ₃ R ₄

R ₂ R ₁

R ₃ R ₄ R ₂

R ₁

R ₃ R ₄ R ₂ Y

R ₁

R ₃ R ₄ R ₂

Br ⁺

H ⁺

OH ₂

-H ⁺ H

R H ⁺ +

H OH ₂

- H ⁺ R

H H ⁺ H

H H ⁺

H H ⁺

OH ₂

- H ⁺ OH

Product(s) Transition state (TS ₁ )

Transition state (TS ₂ )

Delta G ₁

Delta G ₂