ⅣႺ⺞๺ဳ⸅ᇦߩ㐿⊒ߣ⋭ࠛࡀ࡞ࠡ࡯ဳಽሶᄌ឵ᴺߩ⏕┙⎇ⓥઍ⴫⠪ ᄢ㒋ᄢቇⅣႺ቟ో⎇ⓥ▤ℂ࠮ࡦ࠲࡯ ᢎ᝼ ⦼↰⢒਽㧝㧚✜ ⸒╙  ᣖర⚛ߩਛߢߪ #N ߿ $ ߥߤ߇ࡅ࠼࡝࠼ㆶర೷ߣߒߡ೑↪ߐࠇߡ޿ࠆ‫ޔߒ߆ߒޕ‬ࠗࡦࠫ࠙ࡓ⒳߇ㆶర೷ߣߒߡ೑↪ߐࠇࠆߎߣߪ߶ߣࠎߤߥ߆ߞߚ‫ޕ‬ᚒ‫ࡦࠗࡠࡠࠢࠫߪޘ‬ࠫ࠙ࡓࡅ࠼࡝࠼㧔*+P%N㧕߇ᣂⷙߥㆶర೷ߣߒߡ೑↪ߢ߈ࠆߎߣࠍೋ߼ߡႎ๔ߒߚ=?‫ޕ‬࡜ࠫࠞ࡞෻ᔕߦߪ‫ޔ‬ᄙߊߩࠗࠝࡦ෻ᔕߣߪ⇣ߥࠅ‫ޔ‬ਛᕈ᧦ઙਅߢቭ⢻ၮㆬᛯ⊛ߦㅴⴕߔ
ࠆߣ޿߁․ᓽ߇޽ࠆ‫৻ޔߦࠄߐޕ‬ᐲߩᠲ૞ߢⶄᢙߩⅣࠍหᤨߦᒻᚑߢ߈ࠆߥߤߩ೑ὐ߽޽ࠅ‫ޔ‬ᄤὼ‛วᚑߥߤߦᔕ↪ߐࠇߡ޿ࠆ‫࡞ࠞࠫ࡜ߦ߁ࠃߩߎޕ‬෻ᔕߪ㕖Ᏹߦఝࠇߚวᚑᚻᴺߢ޽ࠆ߇‫ࠆ߈ߢߩߣߎࠆ޿↪ޔ‬෻ᔕ೷ߪ੐ታ਄‫࠼࡝࠼ࡅ࠭ࠬ࡞࠴ࡉ࡝࠻ޔ‬㧔$W5P*㧕ߦ㒢ቯߐࠇߡ߅ࠅ‫࡞ࠞࠫ࡜ޔ‬෻ᔕߩߐࠄߥࠆዷ㐿ߩߚ߼ߦ߽ᣂߚߥ⹜⮎߇ᒝߊ᳞߼ࠄࠇ
ߡ޿ࠆ=?‫ߦߢ߹ࠇߎޕ‬ᄙߊߩઍᦧ⹜೷߇ᬌ⸛ߐࠇߡ߈ߚ߇‫ޔ‬෻ᔕᕈ߿ขࠅᛒ޿ᤃߐߥߤߩὐ߆ࠄ‫ࠆ߃⿥ࠍ࠼࡝࠼ࡅ࠭ࠬ࡞࠴ࡉ࡝࠻ޔ‬ታ↪⊛ߥ⹜⮎ߪᧂߛ⷗಴ߐࠇߡ߅ࠄߕ‫᦭ޔ‬ኂᕈࠍ‶†ߦߒߡ↪޿ࠆᔅⷐ߇޽ߞߚ‫ޕ‬ᚒ‫ߩޘ‬㐿⊒ߒߚ *+P%N ߪᄙ᭽ߥ⺞⵾ᴺߦࠃࠅ෻ᔕᕈߩ೙ᓮ߇น⢻ߢ޽ࠆߥߤߩ $W5P* ߦߪή޿․ᕈࠍᜬߞߡ޿ࠆ=?‫࠭ࠬޔߦࠄߐޕ‬ൻว‛ߩਛߢ߽᦭ኂᕈߩૐ޿࡛࠙ൻࠬ࠭ࡅ࠼࡝࠼㧔$W5P+*㧕߽ $W5P* ߦઍࠊࠆ࡜ࠫࠞ࡞ㆶర೷ߣߒߡ૞↪ߒ‫*ޔ‬+P%N ߦ㘃ૃߒߚ෻ᔕᕈࠍ᦭ߔࠆߎߣࠍ⷗಴ߒߚ=?‫ߩࠄࠇߎޕ‬ࡅ࠼࡝࠼ߦࠃࠅ࠻࡝ࡉ࠴࡞ࠬ࠭ࡅ࠼࡝࠼㧔$W5P*㧕ࠍ↪޿ࠆᣢሽߩᣇᴺߢߪਇน⢻ߥ෻ᔕࠍ㆐ᚑߒߚ‫⎇ᧄޕ‬ⓥߢߪᚒ‫߇ޘ‬㐿⊒ߒߚࠫࠢࡠࡠࠗࡦࠫ࠙ࡓࡅ࠼࡝࠼㧔*+P%N㧕‫߅ޔ‬ࠃ࡛߮࠙ൻࠬ࠭ࡅ࠼࡝࠼㧔$W5P+*㧕ㆶర೷ࠍ↪޿ߚᣂⷙߥಽሶᄌ឵෻ᔕߦߟ޿ߡ␜ߔ‫ޕ‬޿ߕࠇ߽ᓥ᧪ᄙᲑ㓏ࠍᔅⷐߣߒߡ޿ߚ෻ᔕߦኻߒߡ‫ޔࡊ࠶࠹ࠬ⋭ޔ‬Ⓩ๺ߥ෻ᔕ᧦ઙࠍ㆐ᚑߒߚ⋭ࠛࡀ࡞ࠡ࡯ဳ෻ᔕߢ޽ࠆ‫ޕ‬㧞㧚ࠫࠛࡦߩࡅ࠼ࡠࠗࡦ࠺࡯࡚ࠪࡦߦࠃࠆࠕ࡝࡞ൻ ࠫࠛࡦߦኻߔࠆ౒ᓎࡅ࠼ࡠࠗࡦ࠺࡯࡚ࠪࡦ߇⿠ߎࠇ߫ࠕ࡝࡞ࠗࡦࠫ࠙ࡓߩ⊒↢߇੍ᗐߐࠇࠆ㧔5EJGOG㧕‫߇ࡓ࠙ࠫࡦࠗ࡞࡝ࠕޕ‬㜞޿᳞ᩭᕈࠍ␜ߔߎߣߪᣢ⍮ߢ޽ࠅ‫ޔ‬ࠞ࡞ࡏ࠾࡞ߥߤߩ᳞㔚ሶ೷ࠍ౒ሽߐߖࠆߎߣߢ‫ޔ‬ㅪ⛯ߒߚࠕ࡝࡞ൻ෻ᔕ߳ߩㆡ↪߇ᦼᓙ
ߢ߈ࠆ=?‫ޕ‬
Scheme 1. Hydroindation of 1,3-dienes and successive allylation.

HInCl2

conjugate addition

Cl2In

㧙㧙Allylation ࠫࠛࡦࠍ಴⊒ߣߒߚࠕ࡝࡞ൻ෻ᔕߩ଀ߪ‫ߦߢ߹ࠇߎޔ‬㜞ଔߥㆫ⒖㊄ዻ⸅ᇦࠍ↪޿ࠆᔅⷐ߇޽ߞߚ‫ߦࠇߎޕ‬ኻߒ‫ޔ‬ᵴᕈൻ೷ࠍᔅⷐߣߖߕߦࡅ࠼ࡠࠗࡦ࠺࡯࡚ࠪࡦ߇⿠ߎࠇ߫‫◲ࠅࠃޔ‬ଢߥࠕ࡝࡞ൻ෻ᔕ♽ߣߥࠆߎߣ߇ᦼᓙߐࠇࠆ‫ࠛࠫ࠲ࡉ࡞࠴ࡔࠫޕ‬ࡦࠍၮ⾰ߦ↪޿ߡᬌ⸛ߒߚ‫↢⊒࠼࡝࠼ࡅࡓ࠙ࠫࡦࠗޕ‬ᴺߪ +P%N$W5P* ♽ࠍណ↪ߒߚ‫ޕ‬ቶ᷷  ᤨ㑆ߩ෻ᔕߢࠕ࡝࡞ࠗࡦࠫ࠙ࡓࠍ⺞⵾ߒ‫ߩߘޔ‬ᓟߦࡌࡦ࠭ࠕ࡞࠺ࡅ࠼ࠍᷝടߔࠆߣࠟࡦࡑ૏ߢㆬᛯ⊛ߦࠕ࡝࡞ൻ߇ㅴⴕߒ‫↢⊛⋡ޔ‬ᚑ‛߇ ෼₸ߢᓧࠄࠇߚ㧔ᑼ 㧕‫ޕ‬

InCl3 + Bu3SnHOHInCl2(2 equiv)(4 equiv)

Cl2In

THF, rt, 5 hJDPhH(1 equiv)
rt, 3 hOH
Ph(1)
94%
ࠕ࡞࠺ࡅ࠼ߦઍ߃ߡ෻ᔕᕈߩૐ޿ࠤ࠻ࡦࠍ↪޿ࠆߣ‫ߩࡓ࠙ࠫࡦࠗ࡞࡝ࠕޔ‬ǫ૏὇⚛ߩ┙૕㓚ኂߩߚ߼ߦૐ෼₸ߢ޽ߞߚ㧔ᑼ 㧕‫ࠍࡦࠛࠫ࠲ࡉޕ‬಴⊒‛⾰ߦ↪޿‫ࠗ࡞࡝ࠕޔ‬ࡦࠫ࠙ࡓߩǫ૏ࠍ৻⟎឵ߣߔࠆߎߣߦࠃࠅ‫ߦࡦ࠻ࠤޔ‬ኻߒߡ߽㜞෼₸ߢ෻ᔕ߇ㅴⴕߒߚ㧔ᑼ 㧕‫ޕ‬O


HInCl2(2 equiv)

THF, rt, 5 hPhMe(1 equiv)

Cl2Inrt, 3 h(4 equiv)

Me OH(2)

Ph15%O
HInCl2(2 equiv) (4 equiv)

PhMe(1 equiv)

Cl2In

THF, rt, 5 hrt, 3 hMe OHPh(3)87% (syn/anti = 79/21)

㧟㧚ࠕ࡟ࡦߩࡅ࠼ࡠࠗࡦ࠺࡯࡚ࠪࡦ
ࠕ࡟ࡦߦߪ෻ᔕὐ߇ਃ▎ᚲሽ࿷ߒ‫ޔ‬૏⟎ㆬᛯᕈߦ⥝๧߇ᜬߚࠇࠆ‫ᦨޕ‬ೋߦࠗࡦࠫ࠙ࡓࡅ࠼࡝࠼ߩᣂⷙ෻ᔕᕈഃ಴ࠍ⋡ᜰߒ‫ޔ‬න⚐ߥࠝࠢ࠴࡞ࠕ࡟ࡦߦኻߔࠆࡅ࠼ࡠࠗࡦ࠺࡯ࠪ
࡚ࡦࠍᬌ⸛ߒߚ=?‫ޕ‬⒳‫↢⊒࠼࡝࠼ࡅࡓ࠙ࠫࡦࠗߩޘ‬ᣇᴺࠍ⹜ߒߚ⚿ᨐ‫ޔ‬+P%N'V5K* ♽߇ᦨ߽ല₸ࠃߊ૞↪ߒ‫㉄ޔ‬ಣℂᓟߦ‫ޔ‬ਃ⒳㘃ߩࠕ࡞ࠤࡦߩ↢ᚑ߇⏕⹺ߢ߈ߚ㧔5EJGOG㧕‫ޕ‬ࡊࡠ࠻ࡦൻߦઍ߃‫ߢ⚛࡛࠙ޔ‬ᓟಣℂߔࠆߣ‫ޔ‬ਛᔃ὇⚛ߦ࡛࠙⚛߇⚿วߒߚ↢ᚑ‛ߩߺ߇ㆬᛯ⊛ߦᓧࠄࠇߚ‫ߩࡦ࡟ࠕ߇ࡓ࠙ࠫࡦࠗޔࠄ߆ߣߎߩߎޕ‬ਛᔃ὇⚛ߦઃടߒߚࠕ࡝࡞࡜ࠫࠞ࡞߇ㆬᛯ⊛ߦ↢ᚑߒߡ޿ࠆߣ⠨߃ࠄࠇࠆ‫ޕ‬㧙㧙

Scheme 2. Hydroindation of allene and succeeding protonation or iodination.

n-C8H17n-C8H17•

InCl3
Et3SiH
Et3B

MeCN
rt, 2 hInCl2+ n-C H

8 17H+InCl2

n-C8H17+I

n-C8H1767%(E/Z =42/58)

22%

n-C8H1765%(E/Z = 57/43)

I2
rt, 0.5 h+n-C8H1720%Iߎߩ૏⟎ㆬᛯᕈߪ‫ޔ‬ᣢሽߩ࡜ࠫࠞ࡞ㆶర೷ߢ޽ࠆ $W5P* ߣߪ⇣ߥߞߡ޿ࠆ‫ޕ‬$W5P* ߢߪ‫⟎ޔ‬឵ၮߩߥ޿ᧃ┵὇⚛߇ࠬ࠲࠾࡞ൻߐࠇߚઃട‛߇ఝవߒߡᓧࠄࠇߚ㧔ᑼ 㧕‫ޕ‬

Bu3SnH
Et3B

n-C8H17•hexanert, 90 hn-C8H17



SnBu3+ n-C8H1720%(E/Z = 65/35)

7%

SnBu3+ n-C8H17

SnBu3 (4)35%ߎߩࠗࡦࠫ࠙ࡓࡅ࠼࡝࠼ߩࠕ࡟ࡦߩਛᔃ὇⚛ߦኻߔࠆ㜞޿෻ᔕᕈ߅ࠃ߮૏⟎ㆬᛯᕈࠍᵴ߆ߒߡಽሶౝߦ᝝ᝒㇱ૏ࠍᜬߟࠕ࡟ࡀࡦߩⅣൻ෻ᔕࠍᬌ⸛ߒߚ㧔ᑼ 㧕‫ࠪࠠࠦ࡞ࠕޕ‬ࠗࡦࠫ࠙ࡓࠍࠗࡦࠫ࠙ࡓࡅ࠼࡝࠼⊒↢ߩ೨㚟૕ߦ↪޿‫ޔ‬Ꮧ㉼᧦ઙߢ෻ᔕߔࠆߎߣߢⅣൻ↢ᚑ‛ߢ޽ࠆ 6*( ⺃ዉ૕߇ቯ㊂⊛ߦᓧࠄࠇߚ‫⺃ࡦ࠲ࡦࡍࡠࠢࠪޔߚ߹ޕ‬ዉ૕߽หߓ෻ᔕ᧦ઙߢല₸ࠃߊวᚑߢ߈ߚ㧔ᑼ 㧕‫♽߇࠼࡝࠼ࡅࡓ࠙ࠫࡦࠗߪߢ♽ᧄޕ‬ਛߢᓢ‫↢⊒ߦޘ‬ߔࠆߚ߼‫ޔ‬ਛ㑆૕࡜ࠫࠞ࡞ߩ᳓⚛ൻ߇ᛥ߃ࠄࠇ‫ޔ‬ല₸⊛ߦⅣൻ߇ㅴⴕߒߡ޿ࠆ‫ޕ‬



Ph•



THFrt, 20 hO



InCl2OMe
PhSiH3
Et3B

InCl2HPhO

THF (0.5 M)
THF (0.1 M)


Ph•


 EtOOC

COOEt

InCl2OMe
PhSiH3Et3B
THF (0.1 M)
rt, 20 h

InCl2(5)O
47% (dr = 87/13)>99% (dr = 87/13)
HPh

EtOOC

Ph

H+COOEt

Ph

H+(6)
EtOOC

COOEt

81% (dr = 56/44)

㧙㧙㧠㧚ࠕ࡟ࡦߩࡅ࠼ࡠࠬ࠲ࡀ࡯࡚ࠪࡦ৻ᣇ‫ޔ‬ᚒ‫࠭ࠬޔߪޘ‬਄ߦࡂࡠࠥࡦࠍᜬߟ࡛࠙ൻࠫࡉ࠴࡞ࠬ࠭ࡅ࠼࡝࠼ $W5P+* ߇‫ޔ‬ࠕ࡞ࠠࡦߥߤߩᄙ㊀⚿วߦ૏⟎ㆬᛯ⊛ߦઃടߔࠆߎߣࠍႎ๔ߒߡ޿ࠆ=?‫ߩߎޕ‬⍮⷗ߦၮߠ޿ߡ $W5P+* ࠍࠕ࡟ࡀࡦߩⅣൻ෻ᔕߦㆡ↪ߒߚߣߎࠈ‫ޔ‬Ⅳൻߪਛ⒟ᐲߩ෼₸ߢㅴⴕߒߚ߇‫ޔ‬Ꮧ㉼᧦ઙߦ߅޿ߡ߽㎮⁁ߩઃട‛߇ ෼₸ߢ೽↢ߒߚ㧔ᑼ 㧕‫ߪࠇߎޕ‬Ⅳൻ೨ߩਛ㑆૕࡜ࠫࠞ࡞߇ࠬ࠭ࡅ࠼࡝࠼ߦࠃߞߡ᳓⚛ൻߐࠇߚߚ߼ߣ⠨߃ࠄࠇࠆ‫ࠄ߇ߥߒ߆ߒޕ‬ࠕ࡟ࡦㇱಽ߳ߩઃടߦᵈ⋡ߔࠆߣ‫ߣ࠼࡝࠼ࡅࡓ࠙ࠫࡦࠗޔ‬หߓ૏⟎ㆬᛯᕈࠍ␜ߒ‫ޔ‬ਛᔃ὇⚛߇ࠬ࠲࠾࡞ൻߐࠇߚઃട‛ߩߺ߇ᓧࠄࠇߡ޿ߚ‫ޕ‬ᣢߦ␜ߒߚࠃ߁ߦߎߩ૏⟎ㆬᛯᕈߪ‫ޔ‬ᣢሽߩ $W5P* ♽ߣߪ⇣ߥࠆ‫࡞࠾࠲ࠬޕ‬ൻߩ႐ว‫ޔ‬㊄ዻ㧙὇⚛⚿ว߇଻ᜬߐࠇߚ⁁ᘒߢ቟ቯߦන㔌‫ޔ‬ขࠅᛒ޿߇ߢ߈‫⺃ߊ⛯ޔ‬ዉ෻ᔕߦዷ㐿ߢ߈ࠆ೑ὐ߇޽ࠆ‫࡛࠙ޕ‬ൻࠬ࠭ࡅ࠼࡝࠼ߪⅣൻ෻ᔕߦߪㆡߐߥ޿߇‫ޔ‬ਛᔃ὇⚛ㆬᛯ⊛ઃടߦࠃࠆౝㇱࡆ࠾࡞ࠬ࠭ߩวᚑ
ᴺߣߒߡߪఝࠇߡ޿ࠆߎߣࠍ⷗಴ߒߚ=?‫ޕ‬SnIBu2Ph•

Bu2SnIH (2 equiv)

Ph(7)+THF (0.1 M)
rt, 20 hOSnIBu2PhO
26%

O
42%

5EJGOG ߦߎࠇ߹ߢߦႎ๔ߐࠇߡ޿ࠆ࠻࡝ࠕ࡞ࠠ࡞ࠬ࠭ࡅ࠼࡝࠼ߦࠃࠆࠕ࡟ࡦߩࡅ࠼ࡠࠬ࠲࠾࡞ൻߩ଀ࠍ␜ߔ‫ޕ‬ᵴᕈൻᴺߦࠃߞߡ↢ᚑ‛߇ᄌൻߔࠆ߇‫ޔ‬ਛᔃ὇⚛߇ࠬ࠲࠾࡞
ൻߐࠇߚDEੑ⟎឵ࡆ࠾࡞ࠬ࠭ࠍᓧࠆߎߣ߇ᦨ߽࿎㔍ߢ޽ࠅ‫ޔ‬໑৻‫ޔ‬2J5P*'V$ ♽ߦࠃࠆ࡜ࠫࠞ࡞෻ᔕߢਛ⒟ᐲߩㆬᛯᕈߢᓧࠄࠇߡ޿ࠆ‫↢ߩߎޕ‬ᚑ‛ߪ‫࠭ࠬ࡞࠾ࡆޔ‬วᚑߦㅢᏱ↪޿ࠄࠇࠆࠕ࡞ࠠࡦߩࡅ࠼ࡠࠬ࠲࠾࡞ൻ╬ߩᚻᴺߢวᚑߔࠆߎߣߪ࿎㔍ߢ޽ࠆ‫ޕ‬
Scheme 3. Hydrostannation of allenes.
Pd(PPh3)4(5 mol%)

n-C8H17

•

n-C8H17

n-C8H17n-C 10H21•

Ph3SnH

Et3B(10 mol%)

Sn = Bu3SnH

HBu3SnH
B(C6F5)3(20 mol%)

78%(E/Z = 33/67)

Sn37%
SnY. Yamamoto, J. Org. Chem. 1997, 62, 2963-2967.
Hn-C10H21

Sn
H+ n-C10H21

Sn+ n-C10H21

Sn
H

51%
10%5%
(E/Z = 66/34)
K. Oshima, Bull. Chem. Soc. Jpn. 1988, 61, 2693-2695.

㧙㧙ߎߩࠃ߁ߥ⢛᥊߆ࠄ‫࡛࠙ޔ‬ൻࠬ࠭ࡅ࠼࡝࠼ߩࠕ࡟ࡦਛᔃ὇⚛߳ߩ㜞޿ㆬᛯᕈߦᵈ⋡ߒ‫ޔ‬DEੑ⟎឵ࡆ࠾࡞ࠬ࠭ߩㆬᛯ⊛วᚑࠍ⹜ߺߚ‫ߩߎޕ‬෻ᔕ߇㆐ᚑߐࠇࠇ߫‫ޔ‬ㅪ⛯ߒߚࠞ࠶ࡊ࡝ࡦࠣ෻ᔕࠍ⚵ߺวࠊߖࠆߎߣߢ‫ߥ↪᦭ޔ‬෻ᔕᚻᴺߣߥࠆ੐߇ᦼᓙߐࠇࠆ‫ޕ‬ᬌ⸛ߩ⚿ᨐ‫੍ޔ‬ᗐㅢࠅߩ૏⟎ㆬᛯ⊛෻ᔕ߇㆐ᚑߐࠇߚ‫┙ޕ‬૕ㆬᛯᕈߪࠕ࡟ࡦߩ⟎឵ၮߦࠃࠆᄢ߈ߥ㆑޿߇⹺߼ࠄࠇ‫ޔ‬፾㜞޿ਃ⚖ࠕ࡞ࠠ࡞ၮߩ⚿วߒߚࠕ࡟ࡦߢߪ૏⟎ㆬᛯ⊛‫┙ޔ‬૕ㆬᛯ⊛ߦ෻ᔕ߇ㅴⴕߒDEੑ⟎឵ࡆ࠾࡞ࠬ࠭߇ ' ૕ㆬᛯ⊛ߦᓧࠄࠇߚ㧔ᑼ 㧕‫࠻ࡔޔߚ߹ޕ‬ࠠࠪࠕ࡟ࡦߢߪ⢽⢌ᣖࠕ࡟ࡦߣߪ┙૕߇ㅒォߒ‫ <ޔ‬૕ߩDEੑ⟎឵ࡆ࠾࡞ࠬ࠭߇ਥ↢ᚑ‛ߣߥߞߚ㧔ᑼ 㧕‫ޕ‬•

Ph+Bu2SnIH



SnIBu2THF, rt, 44 h

PhH(8)+PhH

SnIBu22%70% (E/Z = 90/10)

MeO

•

+Bu2SnIH



THF, rt, 21 h

MeO
SnIBu2

SnIBu2

57% (E/Z = 5/95)

(9)+ MeO
2%਄⸥ߩ࡛࠙ൻࠬ࠭ࡅ࠼࡝࠼ߦࠃࠆࡅ࠼ࡠࠬ࠲࠾࡞ൻߩᯏ᭴ࠍ 5EJGOG ߦ␜ߔ‫ᦨޕ‬ೋߦ࡛࠙ൻࠬ࠭࡜ࠫࠞ࡞߇ࠕ࡟ࡦߩਛᔃ὇⚛ߦઃടߒߡ቟ቯߥࠕ࡝࡞࡜ࠫࠞ࡞߇⊒↢ߔࠆ‫ޕ‬⛯޿ߡ┙૕㓚ኂࠍㆱߌߡᧃ┵὇⚛߇᳓⚛ൻߐࠇࠆߚ߼ߦౝㇱࡆ࠾࡞ࠬ࠭߇ᓧࠄࠇࠆ‫⟎ޕ‬឵ၮ߇፾㜞޿ਃ⚖ࠕ࡞ࠠ࡞ၮߩ႐วߦߪ┙૕㓚ኂߩߚ߼ ' ૕ࡆ࠾࡞ࠬ࠭߇ᓧࠄࠇ‫ޔ‬฽㉄⚛⟎឵ၮࠍᜬߟၮ⾰ߢߪಽሶౝ㈩૏ߦࠃࠅ‫ <ޔ‬૕ࡆ࠾࡞ࠬ࠭߇ㆬᛯ⊛ߦ↢ᚑߔࠆ‫ޕ‬
Scheme 4. Plausible mechanism of hydrostannation by Bu2SnIH.
HSnIBu2

Ph
SnIBu2
Ph85%(E/Z = 91/9 )H SnIBu2

- SnIBu2R•
H SnIBu2

SnIBu2MeO

SnIBu2

H- SnIBu2

MeO
SnIBu2
64%(E/Z = 6/94)

㧙㧙ᰴߦ‫ࠍ࠭ࠬ࡞࠾ࡆߩࠄࠇߎޔ‬න㔌ߔࠆߎߣߥߊࡢࡦࡐ࠶࠻ߢ‫࡛࠙ޔ‬ൻࡌࡦ࠯ࡦߣߩࠞ࠶ࡊ࡝ࡦࠣ෻ᔕࠍ⹜ߺߚ‫↢ࠣࡦ࡝ࡊ࠶ࠞߩࠇߕ޿ޕ‬ᚑ‛߽ࡅ࠼ࡠࠬ࠲࠾࡞ൻߩ┙૕ൻቇࠍ෻ᤋߒߚ߽ߩߣߥߞߚ‫ߜࠊߥߔޕ‬፾㜞޿ਃ⚖ࠕ࡞ࠠ࡞⟎឵ࠕ࡟ࡦߩ෻ᔕߢߪ‫ 'ޔ‬૕ࡆ࠾࡞ࠬ࠭↱᧪ߩ ' ૕ਃ⟎឵ࠕ࡞ࠤࡦ߇ㆬᛯ⊛ߦᓧࠄࠇߚ㧔ᑼ 㧕‫ࠪࠠ࠻ࡔޕ‬ၮࠍ฽߻ੑ⟎឵ࠕ࡟ࡦߩ෻ᔕߢߪ‫ <ޔ‬૕ࡆ࠾࡞ࠬ࠭↱᧪ߩ < ૕ࠕ࡞ࠤࡦࠍㆬᛯ⊛ߦวᚑߔࠆߎߣ߇ߢ
߈ߚ㧔ᑼ 㧕‫ߦ․ޕ‬ੑ⟎឵ࠕ࡟ࡦࠍ↪޿ߚ႐วߪ‫⟎ߩߡߴߔޔ‬឵ၮ߇⇣ߥࠆ྾⟎឵ࠕ࡞ࠤࡦࠍวᚑߔࠆߎߣ߇น⢻ߢ޽ࠆ‫ޕ‬


•




Bu2SnIH

PhI
Pd2(dba)3-CHCl3
Ph3P
TBAF

THF
rt, 11 h

80 oC, 12 h

Bu2SnIH

as above

PhPh

OMen-C8H17•

55%(E/Z = 91/9)

3%OMeOMePhn-C8H17

THFrt, 18 h++n-C8H1762%(E/Z = 1/>99)

(10)

(11)
Ph2%

㧡㧚ࡔ࠴࡟ࡦࠪࠢࡠࡊࡠࡄࡦߩࡅ࠼ࡠࠬ࠲ࡀ࡯࡚ࠪࡦࠕ࡟ࡦ㘃✼૕ߢ޽ࠆࡔ࠴࡟ࡦࠪࠢࡠࡊࡠࡄࡦ߽෻ᔕߦ㑐ਈߔࠆ὇⚛߇ⶄᢙሽ࿷ߒઃടㆬᛯᕈߦ⥝๧߇ᜬߚࠇࠆ‫ޕ‬ᬌ⸛ߩ⚿ᨐ‫ߩࡦࡄࡠࡊࡠࠢࠪࡦ࡟࠴ࡔޔ‬ㆬᛯ⊛ߥࡅ࠼ࡠࠬ࠲
࠾࡞ൻ߇㆐ᚑߢ߈ߚ=?‫ࡦࡄࡠࡊࡠࠢࠪޕ‬Ⅳ਄߇ࡈࠚ࠾࡞ၮߢ⟎឵ߐࠇߚၮ⾰ߩ෻ᔕࠍᑼ ߦ␜ߔ‫ޕ‬$W5P+* ߦࠃࠆ෻ᔕߢߪ‫ޔ‬㐿Ⅳ↢ᚑ‛߇ ߩ෼₸ߢᓧࠄࠇߚ‫࡛࠙ޕ‬ൻࠬ࠭࡜ࠫࠞ࡞߇ౝㇱ὇⚛ߦઃടߒߡࠪࠢࡠࡊࡠࡇ࡞ࡔ࠴࡞࡜ࠫࠞ࡞߇↢ᚑߒߚᓟ‫ޔ‬㐿Ⅳ⇣ᕈൻߒߚߣ⠨߃ࠄࠇࠆ‫↢ޕ‬ᚑ‛ߪ‫ࡦࡄࡠࡊࡠࠢࠪޔ‬Ⅳߩࡈࠚ࠾࡞ၮߩሽ࿷ߔࠆ஥ߩ⚿ว߇㐿ⵚߒߚ߽ߩߢ޽ߞߚ‫᦭ޕ‬ᯏ㊄ዻ⒳ߣࡔ࠴࡟ࡦࠪࠢࡠࡊࡠࡄࡦߩ෻ᔕߢ‫⟎ޔ‬឵ၮ஥ߩ⚿ว߇ㆬᛯ⊛ߦ㐿ⵚߒߚೋ߼ߡߩ଀ߢ޽ࠆ‫ޕ‬

Sn



Bu2SnIH
Et3B (0.1 equiv)

PhTHF, rt, 14 hSnIBu2
PhSnIBu2Ph

HPhSnIBu2(12)81%৻ᣇ‫ޔ‬ᣢሽߩ⹜⮎ߢ޽ࠆ $W5P* ߩ෻ᔕߢߪ‫┵ᧃ߇࠭ࠬޔ‬὇⚛ߦઃടߒߚ↢ᚑ‛߇ᓧࠄࠇߚ㧔ᑼ 㧕‫⚿ߩࠄࠇߎޕ‬ᨐ߆ࠄ‫࡛࠙ޔ‬ൻࠬ࠭ࡅ࠼࡝࠼ߪ․᦭ߩ૏⟎ㆬᛯᕈࠍ␜ߒ‫ޔ‬ౝㇱ὇⚛ࠍㆬᛯ⊛ߦࠬ࠲࠾࡞ൻߔࠆߎߣ߇⏕⹺ߐࠇߚ‫ޕ‬㧙㧙Sn
Bu3SnH
Et3B (0.1 equiv) Phhexane, rt, 65 h

HSnBu3

SnBu3(13)

Ph

Ph

33%

ࠕ࡟ࡦߣห᭽ߦ‫࡞࠾࠲ࠬࡠ࠼ࡅߩࡦࡄࡠࡊࡠࠢࠪࡦ࡟࠴ࡔޔ‬ൻ↢ᚑ‛߽‫ޔ‬ㅪ⛯ߒߚࠞ࠶ࡊ࡝ࡦࠣ෻ᔕ߳ߩዷ㐿߇น⢻ߢ޽ߞߚ㧔ᑼ 㧕‫ޕ‬Bu2SnIH
Et3B

 Ph(a)

THF, rt
16 h

SnIBu2Ph

p-IC6H4NO2
Pd cat.
Ph3P
TBAF
80 oC, 10 h

C6H4NO2-pPh(14)92%એ਄ߩࠃ߁ߦᧄ⎇ⓥߢߪᣂߚߥ࡜ࠫࠞ࡞෻ᔕߩ㐿⊒ࠍ⋡⊛ߣߒߡ‫࡝࠼ࡅࡓ࠙ࠫࡦࠗޔ‬࠼㧔*+P%N㧕‫࡛࠙߮ࠃ߅ޔ‬ൻࠫࡉ࠴࡞ࠬ࠭ࡅ࠼࡝࠼㧔$W5P+*㧕ߩวᚑ⊛೑↪ᴺߩᬌ⸛ࠍⴕߞߚ‫⚿ߩߘޕ‬ᨐ‫ޔ‬ᣢሽߩઍ⴫⊛ߥ࡜ࠫࠞ࡞⹜⮎ߢ޽ࠆ࠻࡝ࡉ࠴࡞ࠬ࠭ࡅ࠼࡝࠼
㧔$W5P*㧕ߢߪਇน⢻ߥ෻ᔕࠍ㆐ᚑߒߚ‫ޕ‬⻢ㄉᧄ⎇ⓥߪ㧶㧲㧱㧞㧝਎♿⽷࿅ߩ⎇ⓥഥᚑߦࠃࠅㆀⴕߐࠇߚ߽ߩߢ޽ࠆ‫ߦߎߎޕ‬㧶㧲㧱㧞㧝਎♿⽷࿅ߦኻߒߡᷓߊᗵ⻢↳ߒ਄ߍࠆᰴ╙ߢ޽ࠆ‫ޕ‬ෳ⠨ᢥ₂
[1] Baba, A.; Shibata, I. Chem. Rec. 2005, 5, 323-335.
[2] Baba, A. Shibata, I.; Yasuda, M. In Comprehensive Organometallic Chemistry III, Crabtree, R.
H.; Michael, D.; Mingos P. Eds, Elsevier: Oxford 2006; Vol. 9, Chapter 8, 341-380.

[3] (a) Miyai, T.; Inoue, K.; Yasuda, M.; Shibata, I.; Baba, A. Tetrahedron Lett. 1998, 39,1929-1932. (b) Inoue, K.; Sawada, A.; Shibata, I.; Baba, A. Tetrahedron Lett. 2001, 42,4661-4663.(c) Inoue, K.; Sawada, A.; Shibata, I.; Baba, A. J. Am. Chem. Soc. 2002, 124,906-907.
[4] Shibata, I.; Baba, A. Curr. Org. Chem. 2002, 6, 665-693.
[5] Hayashi, N.; Honda, H.; Yasuda, M.; Shibata, I.; Baba, A. Org. Lett. 2006, 8, 4553-4556.
[6] Hayashi, N.; Hirokawa, Y.; Shibata, I.; Yasuda, M.; Baba, A. Org. Biomol. Chem. 2008, 6,1949-1954.

[7] Shibata, I.; Suwa, T.; Ryu, K.; Baba, A. J. Am. Chem. Soc. 2001, 123, 4101-4102.
[8] Hayashi, N.; Kusano, K.; Sekizawa, S.; Shibata, I.; Yasuda, M.; Baba, A. Chem. Commun.
2007, 4913-4915.

[9] Hayashi, N.; Hirokawa, Y.; Shibata, I.; Yasuda, M.; Baba, A. J. Am. Chem. Soc. 2008, 130,2912-2913.

㧙㧙